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JS17R8C'dPCT/PT0 2 0 JUN 2001 



INTERNATIONAL APPLICATION NO. 
PCT/EP99/09912 



TITLE OF INVENTION NICKEL MIXED HYDROXIDE, METHOD FOR PRODUCING THE SAME, AND THE 
USE THEREOF AS A CATHODE MATERIAL IN ALKALINE BATTERIES 



APPLICANT(S) FOR DO/EO/US 1) Viktor Stoller; 2) Armin Olbrich; 3) Juliane Meese-Marktscheffel; 
4) Mareret Wohlfahrt-Mehre ns; 5) Peter Axmann; 6) Herbert Dittrich; 7) Michael Kasper; 8) S andra Strobele 

— — s — : : — : ■ — -; r-r-r — , r%--: *_jfr?i *„j r\pf:„<> /nn/cn/f IC^ tVi<i fnllnwina \tcm<i and other i 



■70-1390 US DEPARTMEMT OF COMMERCE PATENT AND TRADEMARK OFFICE 

1-2000) 

TRANSMITTAL LETTER TO THE UNITED STATES 
DESIGNATED/ELECTED OFFICE (DO/EO/US) 
CONCERNING A FILING UNDER 35 U.S.C. 371 



INTERNATIONAL FILING DATE 
14 December 1999 (14.12.99) 



ATTORNEY'S DOCKET NUMBER 

MO-6398/STA-154 



To be Assigned 



PRIORITY DATE CLAIMED 
24 December 1998 (24T2.98) 



Applicant herewith submits to the United States Designated/Elected Office (DO/EO/US) the following items and other information: 

1. [3 This is a FIRST submission of items concerning a filing under 35 U.S.C. 371. 

2. \~\ This is a SECOND or SUBSEQUENT submission of items concerning a filing under 35 U.S.C. 371. 
This is an express request to begin national examination procedures (35 U.S.C. 371(1)). The submission must include 
items (5), (6), (9) and (21) indicated below. 

4.l2Cj The US has been elected by the expiration of 19 months from the priority date (Article 31). 
S.fxl A copy of the International Application as filed (35 U.S.C. 371(c)(2)) 

a. H is attached hereto (required only if not communicated by the International Bureau). 

b. □ has been communicated by the International Bureau. 

c. □ is not required, as the application was filed in the United States Receiving Office (RO/US), 
|6.[xl An English language translation of the International Application as filed (35 U.S.C. 371(c)(2)). 

a. [x] 's attached hereto. 

b. □ has been previously submitted under 35 U.S.C. 154(d)(4). 

Amendments to the claims of the International Aplication under PCT Article 19 (35 U.S.C. 371(c)(3)) 
a- □ are attached hereto (required only if not communicated by the International Bureau). 

b. □ have been communicated by the International Bureau. 

c. □ have not been made; however, the time limit for making such amendments has NOT expired. 

d. n have not been made and will not be made. 

8. n An English language translation of the amendments to the claims under PCT Article 19 (35 U.S.C. 371 (c)(3)). 

9. [xl An oath or declaration of the inventor(s) (35 U.S.C. 371(c)(4)). 

10, □ An English lanugage translation of the annexes of the International Preliminary Examination Report under PCT 
Article 36 (35 U.S.C. 371(c)(5)). 

Items 11 to 20 below concern document(s) or information included: 

1 l.Q An Information Disclosure Statement under 37 CFR 1.97 and 1.98. 

12. [xj An assignment document for recording. A separate cover sheet in compliance with 37 CFR 3.28 and 3.31 is included. 

13. [X] A FIRST preliminary amendment. 

14. n A SECOND or SUBSEQUENT preliminary amendment. 

15. L] A substitute specification. 

16. A change of power of attorney and/or address letter. 

17. Q A computer-readable form of the sequence listing in accordance with PCT Rule 13ler.2 and 35 U.S.C. 1.821 - 1.825. 

18. [X] A second copy of the published international application under 35 U.S.C. 154(d)(4). 

19-D A. second copy of the English language translation of the international application under 35 U.S.C. 154(d)(4). 

20. fx] Other items or informafion: 

Preliminary Amendment w/ Abstract; PTO Form 1449 and references listed therein; 
5 pages of drawings containing Figs. 1-7 



page I of 2 



JCISees'dPOT/PTG 2 0 JUN 2001 



u s. APPl,l«i\TI*W Na (il k 

To be ^Jswipd f 



INTERNA nONAL APPLICATION NO 

PCT/EP99/Q9912 



ATTORNCVS DOCKET NUMBER 

Mo-6398/STA 154 



- SIOOO.OO 
. $860.00 



21. jx] The following fees are submitted: 
BASIC NATIONAL FEE (37 CFR 1.492 (a) (1) - (5)): 
Neither international preliminary examination fee (37 CFR 1.482) 
nor international search fee (37 CFR 1.445(a (2)) paid to USPTO 
and International Search Report not prepared by the EPO or JPO 

International preliminary examination fee (37 CFR 1.482) not paid to 
USPTO but International Search Report prepared by the EPO or JPO • 

International preliminary examination fee (37 CFR 1 482) not paid to USPTO 

but international search fee (37 CFR 1.445(a)(2)) paid to USPTO S710.00 

International preliminary examination fee (37 CFR 1.482) paid to USPTO 

but all claims did not satisfy provisions of PCT Article 33(l)-(4) $690.00 

International preliminary examination fee (37 CFR 1.482) paid to USPTO 

and all claims satisfied provisions of PCT Article 33(l)-(4) $100.00 

ENTER APPROPRIATE BASIC FEE AMOUNT = 



Surcharge of S130.00 for furnishing the oath or declaration later than Q 20 \~] 30 
months from the earliest claimed priority date (37 CFR 1.492(e)). 



CALCULATIONS PTO USE ONLY 



860.00 



CLAIMS 



Total claims 



NUMBER FILED 



13 



-20 = 



NUMBER EXTRA 



0 



RATE 



X $18.00 



0.00 



independent claims 



-3 = 



X $80.00 



0.00 



14ULTIPLE DEPENDENT CLAIM(S) (if applicable) 



+ $270.00 



0.00 



TOTAL OF ABOVE CALCULATIONS = 



860.00 



~| Applicant claims small entity status. See 37 CFR 1.27. The fees indicated above 
— are reduced by 1/2. 



0.00 



SUBTOTAL 



^Processing fee of $130.00 for furnishing the English translation later than [^20 Q 30 
'months from the earliest claimed priority date (37 CFR 1.492(f)). 



860.00 



TOTAL NATIONAL FEE = 



860 .0 0 



Fee for recording the enclosed assignment (37 CFR 1.21(h)). The assignment must be 
accompanied by an appropriate cover sheet (37 CFR 3.28, 3.31). $40.00 per property + 



40.00 



TOTAL FEES ENCLOSED = 



Amount to be 
refunded: 



charged: 



a. Q A check in the amount of $ . 



b. m Please charge my Deposit Account No. 13-3848 
A duplicate copy of this sheet is enclosed. 



to cover the above fees is enclosed. 
in the amount of $900^.00_ 



to cover the above fees. 



c. Ixl T'he Commissioner is hereby authorized to charge any additional fees which may be required, or credit any 

overpayment to Deposit Account No. 13-3848 A duplicate copy of this sheet is enclosed. 

d. n Fees are to be charged to a credit card. WARNING: Information on this form may become public. Credit card 

information should not be included on this form. Provide credit card information and authorization on PTO-2038. 

NOTE: Where an appropriate time limit under 37 CFR 1.494 or 1.495 has not faten me*, a pi 
1.137 (a) or (b)) must be filed and granted to restore the application to pending statu, 

SEND ALL CORRESPONDENCE TO 

Diderico van Eyl 
Bayer Corporation 
Patent Department 
100 Bayer Road 
Pittsburgh, PA 15205-9741 
USA 



00157 

PATENT TRADEMARK OFFICE 




REGISTRATION NUMBER 



FORM PTO-1390 (REV 11-2000) page 2 of 2 



09/868995 



JGtSRec'dPOWTO 2 0 JUH 2001 



PATENT APPLICATION 

Mo-6398 

STA-154 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



APPLICATION OF 



PCT/EP 99/09912 



VIKTOR STOLLER ET AL 



SERIAL NUMBER: TO BE ASSIGNED 



FILED: 



HEREWITH 



TITLE: 



NICKEL MIXED HYDROXIDE, 
METHOD FOR PRODUCING 
THE SAME, AND THE USE 
THEREOF AS A CATHODE 



MATERIAL IN ALKALINE BATTERIES 



PRELIMINARY AMENDMENT 



Assistant Commissioner for Patents 

Washington, D.C. 20231 

Sir: 

Upon the granting of a Serial Number and filing date, please amend the 
subject patent application as follows: 




IN THE CLAIMS 

Please cancel Claims 1-11, and add new Claims 12-24: 

~ 12. Nickel mixed hydroxide with Ni as the main element and with a 

layer structure, comprising 

a) at least one element Ma from the group comprising Fe, Cr, Co, Ti, Zr 
and Cu which is present in two different oxidation states which differ by 
one electron in terms of the number of outer electrons; 

b) at least one element Mb from the group comprising B, Al, Ga, In and 
rare earth metals present in the trivalent oxidation state; 

c) optionally at least one element Mc from the group comprising Mg, Ca, 
Sr, Ba and Zn present in the divalent oxidation state; 

d) apart from the hydroxide, at least one additional anion selected from 
the group consisting of halides, carbonate, sulfate, acetate, oxalate, 
borate and phosphate in a quantity sufficient to preserve the 
electroneutrality of the mixed hydroxide; and 

e) water of hydration in a quantity which stabilizes the relevant structure 
of the mixed hydroxide. 

13. The nickel mixed hydroxide according to Claim 12, wherein the 
proportion of Ni is from 60 to 92 mol % and the total proportion of the elements Ma, 
Mb and Mc is from 40 to 8 mol %, in each case based on the total amount of Ni, Ma, 
Mb and Mc. 

14. The nickel mixed hydroxide according to Claim 12, wherein the 
proportion of the element Ma is from 10 to 40 mol %, based on the total amount of 
the elements Ma, Mb and Mc. 

15. The nickel mixed hydroxide according to Claim 12, wherein the 
proportion of the element Mc is from 1 to 30 mol %, based on the total amount of 
elements Mg, Mb and Mc. 



Mo-6398 



-2- 



16. The nickei mixed hydroxide according to Claim 12, wherein the degree 
of oxidation a of the element Ma, defined according to the following formula (1), is 
from 0.01 to 0.99 

« = (I). 

wherein Ma"^''^^' means the molar quantity of the element Mg in the higher oxidation 
state, and Mg ^'''^ the molar quantity of the element Ma in the lower oxidation state, 
and X is a number between 1 and 3. 

17. The nickel mixed hydroxide according to Claim 12, wherein the nickel 
mixed hydroxide is in the form of a powder with an average particle size from 1 to 
100 }am. 

18. The nickel mixed hydroxide according to Claim 12, wherein the rare 
earth metals of the element Mb are selected from the group consisting of SC, Y and 
La. 

19. The nickel mixed hydroxide according to Claim 12, wherein the halides 
are selected from the group consisting of fluoride and chloride. 

20. The nickel mixed hydroxide according to Claim 12, wherein the nickel 
mixed hydroxide is a cathode material in an alkaline battery. 

21 . A process for preparing a nickel mixed hydroxide with Ni as the 
main element and with a layer structure, comprising: 

a) at least one element Ma selected from the group consisting of Fe, Cr, 
Co, Ti, Zr and Cu which is present in two different oxidation states 
which differ by one electron in terms of the number of outer electrons; 

b) at least one element Mb from selected from the group consisting of B, 
Al, Ga, In and rare earth metals present in the trivalent oxidation state; 

c) optionally at least one element Mc selected from the group consisting 
of Mg, Ca, Sr, Ba and Zn present in the divalent oxidation state; 



Mo-6398 



-3- 



d) apart from the hydroxide, at least one additional anion selected from 
the group consisting of halides, carbonate, sulfate, acetate, oxalate, 
borate and phosphate in a quantity sufficient to preserve the 
electroneutrality of the mixed hydroxide; and 

e) water of hydration in a quantity which stabilizes the relevant structure 
of the mixed hydroxide, 

the process comprising reacting components required to obtain the 
relevant mixed hydroxides in the form of water-soluble salts of Nl and of the 
elements Ma, Mb and optionally Mc in a basic, aqueous medium for the co- 
precipitation of hydroxide reaction products with the formation of a homogeneous 
suspension of said reaction products, 

wherein either water-soluble salts of the element Ma are used in different 
oxidation states or a water-soluble salt of the element Ma is used in the lower 
oxidation state and a partial oxidation is carried out until the desired ratio is obtained 
between the different oxidation states of the element Mg, or a water-soluble salt of 
the element Ma is used in the higher oxidation state and a partial reduction is carried 
out until the desired ratio is obtained between the different oxidation states of the 
element Ma, separation of the water from the suspension, and drying of the reaction 
products. 

22. The process according to Claim 21 , wherein at least one of the 
reaction components is introduced into the aqueous medium by anodic oxidation of 
the corresponding metal. 

23. The process according to Claim 21 , wherein the reaction Is carried out 
at a pH from 8 to 13. 

24. The process according to Claim 21 , wherein partial oxidation is carried 
out by using oxygen, H2O2, hypochlorite, peroxodisulfates or percarbonates as 
oxidizing agent. ~ 



Mo-6398 



-4- 



IN THE SPECIFICATION 

In page 1, replace the Title with the following Title: 
--NICKEL MIXED HYDROXIDE, METHOD FOR PRODUCING THE SAME, AND 
THE USE THEREOF AS A CATHODE MATERIAL IN ALKALINE BATTERIES- 

In page 1, below the Title, please add: 

-This application is the National Stage Application of PCT/EP99/09912, 
which claims a priority from German Applications 198 60 143.3 filed December 24, 
1998, and 199 39 025.8, filed August 18, 1999.- 

On page 1, above line 5, please add: 

- BACKGROUND - 
On page 3, line 1, above the line beginning with "The invention...," add: 

- DESCRIPTION - 
On page 9, below line 10, please add: 

-The examples below are illustrative examples in which all parts and 
percentages are by weight unless otherwise indicated. ~ 
On page 20, line 13, please add: 

-Although the present invention has been described in detail with reference 
to certain preferred versions thereof, other variations are possible. Therefore, the 
spirit and scope of the appended claims should not be limited to the description of 
the versions contained therein.- 

In the Abstract, replace the Abstract with the following new Abstract, 

submitted herein on a separate page: 

- NICKEL MIXED HYDROXIDE, METHOD FOR PRODUCING THE SAME, 
AND THE USE THEREOF AS A CATHODE MATERIAL IN ALKALINE BATTERIES 

ABSTRACT OF THE DISCLOSURE 
The invention relates to a nickel mixed hydroxide with Ni as the main element 
and with a layer structure, comprising at least one element Ma from the group 
comprising Fe, Cr, Co, Ti, Zr and Cu which is present in two different oxidation 
states which differ by one electron in terms of the number of outer electrons; at least 
one element Mb from the group comprising B, Al, Ga, In and RE (rare earth metals) 
present in the trivalent oxidation state; optionally at least one element Mc from the 



Mo-6398 



-5- 



group comprising iVlg, Ca, Sr, Ba and Zn present in the divalent oxidation state; 
apart from the hydroxide, at least one additional anion from the group comprising 
halides, carbonate, sulfate, oxalate, acetate, borate and phosphate in a quantity 
sufficient to preserve the electroneutrality of the mixed hydroxide; and water of 
hydration in a quantity which stabilizes the relevant structure of the mixed 
hydroxide.- 



Mo-6398 



-6- 



REMARKS 



Entry of this Preliminary Amendment Is requested. The above-made 
amendments have been made to place the application in conformance with U.S. 
standards. No new matter has been added. 



Bayer Corporation 
1 00 Bayer Road 

Pittsburgh, Pennsylvania 15205-9741 
(412) 777-8355 

FACSIMILE PHONE NUMBER: 

(412)777-8363 
s:\kgb\dve276pa 




Diderico van Eyiy 
Attorney for ypeflicants 
Reg. No. 38jB41 



Mo-6398 



-7- 



Mo-6398 
STA-154 

Marked-Up Version to Reflect Changes in the Specification 

IN THE SPECIFICATION 

In page 1, the Title was replaced with the following Title: 
-NICKEL MIXED HYDROXIDE, METHOD FOR PRODUCING THE SAME, AND 
THE USE THEREOF AS A CATHODE MATERIAL IN ALKALINE BATTERIES- 

In page 1, below the Title, the following was added: 

-This application is the National Stage Application of PCT/EP99/09912, 
which claims a priority from German Applications 198 60 143.3 filed December 24, 
1998, and 199 39 025.8, filed August 18, 1999.- 

On page 1 , above line 5, the following heading was added: 

- BACKGROUND - 
On page 3, line 1, above the line beginning with "The invention...," the 
following heading was added: 

- DESCRIPTION - 
On page 9, below line 10, the following was added: 
-The examples below are illustrative examples in which all parts and 
percentages are by weight unless otherwise indicated. - 
On page 20, line 13, the following was added: 

-Although the present invention has been described in detail with reference 
to certain preferred versions thereof, other variations are possible. Therefore, the 
spirit and scope of the appended claims should not be limited to the description of 
the versions contained therein.- 
IN THE CLAIMS 

Claims 1-11 were cancelled and new Claims 12-24 were added: 

— 12. Nickel mixed hydroxide with Ni as the main element and with a 
layer structure, comprising 

a) at least one element Ma from the group comprising Fe, Cr, Co, Ti, Zr 

and Cu which is present in two different oxidation states which differ by 
one electron in terms of the number of outer electrons; 



Mo-6398 



-8- 



b) at least one element Mb from the group comprising B, Ai, Ga, In and 
rare earth metals present in the trivalent oxidation state; 

c) optionally at least one element Mc from the group comprising Mg, Ca, 
Sr, Ba and Zn present in the divalent oxidation state; 

d) apart from the hydroxide, at least one additional anion selected from 
the group consisting of halides, carbonate, sulfate, acetate, oxalate, 
borate and phosphate in a quantity sufficient to preserve the 
electroneutrality of the mixed hydroxide; and 

e) water of hydration in a quantity which stabilizes the relevant structure 
of the mixed hydroxide. 

13. The nickel mixed hydroxide according to Claim 12, wherein the 
proportion of Ni is from 60 to 92 mol % and the total proportion of the elements Mg, 
Mb and Mc is from 40 to 8 mol %, in each case based on the total amount of Ni, Mg, 
Mb and Mc- 

14. The nickel mixed hydroxide according to Claim 12, wherein the 
proportion of the element Mg is from 10 to 40 mol %, based on the total amount of 
the elements Mg, Mb and Mc. 

15. The nickel mixed hydroxide according to Claim 12, wherein the 
proportion of the element Mc is from 1 to 30 mol %, based on the total amount of 
elements Mg, Mb and Mc. 

16. The nickel mixed hydroxide according to Claim 12, wherein the degree 
of oxidation a of the element Ma, defined according to the following formula (I), is 
from 0.01 to 0.99 

a= (I), 

wherein Mg'^*''"'^' means the molar quantity of the element Mg in the higher oxidation 
state, and Mg the molar quantity of the element Mg in the lower oxidation state, 
and x is a number between 1 and 3. 



Mo-6398 



-9- 



17. The nickel mixed liydroxide according to Claim 12, wlierein the nickel 
mixed hydroxide is in the form of a powder with an average particle size from 1 to 
100 ^m. 

18. The nickel mixed hydroxide according to Claim 12, wherein the rare 
earth metals of the element Mb are selected from the group consisting of SC, Y and 
La. 

19. The nickel mixed hydroxide according to Claim 12, wherein the halides 
are selected from the group consisting of fluoride and chloride. 

20. The nickel mixed hydroxide according to Claim 12, wherein the nickel 
mixed hydroxide is a cathode material in an alkaline battery. 

21 . A process for preparing a nickel mixed hydroxide with Ni as the 
main element and with a layer structure, comprising: 

a) at least one element Ma selected from the group consisting of Fe, Cr, 
Co, Ti, Zr and Cu which is present in two different oxidation states 
which differ by one electron in terms of the number of outer electrons; 

b) at least one element Mb from selected from the group consisting of B, 
Al, Ga, In and rare earth metals present in the trivalent oxidation state; 

c) optionally at least one element Mc selected from the group consisting 
of Mg, Ca, Sr, Ba and Zn present in the divalent oxidation state; 

d) apart from the hydroxide, at least one additional anion selected from 
the group consisting of halides, carbonate, sulfate, acetate, oxalate, 
borate and phosphate in a quantity sufficient to preserve the 
electroneutrality of the mixed hydroxide; and 

e) water of hydration in a quantity which stabilizes the relevant structure 
of the mixed hydroxide, 

the process comprising reacting components required to obtain the 
relevant mixed hydroxides in the form of water-soluble salts of Ni and of the 
elements Ma, Mb and optionally Mc in a basic, aqueous medium for the co-precipita- 
tion of hydroxide reaction products with the formation of a homogeneous suspension 
of said reaction products, 

Mo-6398 -10- 



wherein either water-soluble salts of the element Ma are used in different 
oxidation states or a water-soluble salt of the element Ma is used in the lower 
oxidation state and a partial oxidation is carried out until the desired ratio is obtained 
between the different oxidation states of the element Ma, or a water-soluble salt of 
the element Ma is used in the higher oxidation state and a partial reduction is carried 
out until the desired ratio is obtained between the different oxidation states of the 
element Ma, separation of the water from the suspension, and drying of the reaction 
products. 

22. The process according to Claim 21 , wherein at least one of the 
reaction components is introduced into the aqueous medium by anodic oxidation of 
the corresponding metal. 

23. The process according to Claim 21 , wherein the reaction is carried out 
at a pH from 8 to 13. 

24. The process according to Claim 21 , wherein partial oxidation is carried 
out by using oxygen, H2O2, hypochlorite, peroxodisulfates or percarbonates as 
oxidizing agent. 



Mo-6398 



-11- 



-24- 



NICKEL MIXED HYDROXIDE, METHOD FOR PRODUCING 
THE SAME, AND THE USE THEREOF AS A CATHODE 
MATERIAL IN ALKALINE BATTERIES 

ABSTRACT OF THE DISCLOSURE 
The invention relates to a nickel mixed hydroxide with Ni as the 
main element and with a layer structure, comprising at least one element 
Ma from the group comprising Fe, Cr, Co, Ti, Zr and Cu which is present in 
two different oxidation states which differ by one electron in terms of the 
number of outer electrons; at least one element Mu from the group 
comprising B, Al, Ga, In and RE (rare earth metals) present in the trivalent 
oxidation state; optionally at least one element Mc from the group 
comprising Mg, Ca, Sr, Ba and Zn present in the divalent oxidation state; 
apart from the hydroxide, at least one additional anion from the group 
comprising halides, carbonate, sulfate, oxalate, acetate, borate and 
phosphate in a quantity sufficient to preserve the electroneutrality of the 
mixed hydroxide; and water of hydration in a quantity which stabilizes the 
relevant structure of the mixed hydroxide. 



STA 154-FC 



09/868995 



(5 ]ff^1^ 



- 1 - 



JC18ksg'^ 



-^Z^im 2 0 JUN 2001 



Nickel mixed hydroxide, process for the preparation thereof and the use thereof 
as cathode material in allcaline batteries 

The present invention relates to a nickel mixed hydroxide with Ni as the main 
element and with an expanded layer structure, a process for the preparation thereof 
by co-precipitation of the hydroxides in an alkaline medium and to the use thereof as 
cathode material in alkaline batteries. 

p-Nickel(II) hydroxide is used in alkaline accumulators as positive electrode 
material. Changes in certain electrochemical properties may be obtained by 
incorporating foreign ions. 

The incorporation of trivalent ions in the nickel hydroxide matrix in molar 
proportions of >20 mol % leads to a new structure. The materials thus altered have 
the structure of hydro talcite and, in comparison with P-Ni(OH)2, are characterised by 
an expanded layer structure in the intermediate layers of which water and various 
anions are present. The layer expansion alone has a fundamental influence on the 
electrochemistry, in this case on the potential position and electrochemical 
usefulness of the nickel ions. The trivalent cation used in each case exerts an 
additional effect on the electrochemical behaviour of the materials. 

Single-substituent variants containing the substituents Fe, Mn, Co and Al are known 
from the literature. Most have improved utilisation of the nickel ions but their 
stability is not very pronounced. Others, on the other hand, have good cycle stability 
but the nickel utilisation is lov/er. 

Substitution with a combination of two different cations is also found in the 
literature. EP 0 793 285 Al describes nickel hydroxide materials which contain, for 
example, the elements Co or Mn in combination with elements such as, e.g., Fe, Al, 
La and others. Co and Mn are used in divalent form in the preparation of materials. 



STA 154-FC 



-2- 

no oxidising agents being used in the further course of preparation. Where 
preparation takes place by electrochemical (cathodic) deposition, precipitation even 
takes place in a reducing environment due to accompanying hydrogen evolution. Co 
is therefore present in the divalent form in the finished active material, together with 
5 trivalent cations such as Fe, Al, La amongst others The materials are analysed and 
assessed in terms of their potential position during the discharge process and charge 
acceptance at relatively high temperatures, but there are no details whatsoever about 
the cycle stability and actual electrochemical utilisation in the form of absolute 
values. Only relative capacities are given. 

10 

EP 0 712 174 A2 describes nickel hydroxides in which, in contrast to EP 0 793 285 
Al, trivalent instead of divalent Mn ions are used as substituents in combination 
with other trivalent elements such as Al, Fe and Co. Mn is present in the product in 
the trivalent form together with Al, Fe or Co, and it is also possible for Mn to be 

15 present in several oxidation states simultaneously ("mixed valent") in the solid. 
These Mn-containing materials exhibit pronounced cycle stability but the nickel 
utilisation is only slightly above that of the conventional nickel hydroxides. No 
practical indications that the use of mixed valent systems other than Mn may lead to 
an improvement in the capacity and nickel utilisation can be derived fi-om this prior 

20 art. 

The object of the present invention is to provide a nickel mixed hydroxide which, 
whilst having good cycle stability, exhibits a marked improvement in the 
electrochemical utilisation of the nickel ions and the mass-related capacity. 
25 Moreover, a simple process for the preparation of such a nickel mixed hydroxide 
should be given. 

This object is achieved by a nickel mixed hydroxide according to claim 1. 
Advantageous embodiments of the nickel mixed hydroxide according to the 
30 invention are given in subclaims 2 to 6. 



STA 154-FC 



-3 - 

The invention provides, therefore, a nickel mixed hydroxide with Ni as the main 
element and with a layer structure comprising 

a) at least one element Ma from the group comprising Fe, Cr, Co, Ti, Zr and Cu, 
which is present in two different oxidation states which differ by one electron 
in terms of the number of outer electrons; 

b) at least one element Mb present in the trivalent oxidation state from the group 
comprising B, Al, Ga, In and RE (rare earth metals, preferably Sc, Y or La); 

c) optionally at least one element Mc present in the divalent oxidation state 
from the group comprising Mg, Ca, Sr, Ba and Zn; 

d) apart from the hydroxide, at least one additional anion from the group 
comprising halides (preferably fluoride or chloride), carbonate, sulfate, 
acetate, oxalate, borate and phosphate in a quantity at least sufficient to 
preserve the electroneutrality of the mixed hydroxide; and 

e) water of hydration in a quantity that stabilises the relevant structure of the 
mixed hydroxide. 

Surprisingly, it became apparent according to the invention that particularly cycle- 
stable nickel mixed hydroxides with markedly increased nickel utilisation are 
obtained in particular when, apart from nickel, at least two other cations are present 
in the nickel hydroxide matrix, one of which (Ma) is selected from the group 
comprising Fe, Cr, Co, Ti, Zr and Cu, this being present in two different oxidation 
states which differ by one electron in terms of the number of outer electrons, that is, 
in a defined mixed valent form, and the other (Mb) from the group comprising B, Al, 
Ga, In and RE (rare earth metals) is present in the fixed trivalent oxidation state. 



STA 154-FC 



-4- 

Such a material exhibits very good cycle stability in half-cell tests, a maximum 
electronic utilisation of 1.5 electrons per nickel ion being obtained. 

In full-cell tests this material exhibits a utilisation of a constant 1 .5 electrons per 
nickel ion during a measurement over 100 cycles, which corresponds to a specific 
capacity of more than 260 mAh/g. 

The nickel hydroxide materials according to the invention exceed those in which the 
two additional cations (Ni substituents), as described in EP 0 793 285 Al, are 
present in a uniform oxidation state in each case, as shown by an electrochemical 
comparison in the example part below. They also exceed those nickel hydroxide 
materials in which, according to EP 0 712 174 A2, one additional cation is, for 
example, trivalent Al or Co and the other additional cation is Mn, which may be 
present simultaneously in different oxidation states. 

The nickel hydroxide materials according to the invention may be prepared in 
densities favourable for use in secondary batteries, which densities correspond to 
those of P-nickel hydroxides having a regular morphology. 

Without being bound by any particular theory, it may be assumed that several effects 
can be held responsible for these improvements: 

1. It is assumed that lattice defects arise if the various Ni substituents Mb(III), 
Ma(in) and Ma(II) are present in the material. If, for example, the element Ma 
is present in the oxidation states (III)/(n), the proportion of trivalent cations 
and hence the charge of the main layer can be regulated by means of the 
Ma(III)/Ma(n) ratio. The anion and water content of the structure depend on 
the latter. In hydrotalcite compounds, the anions in the interlayer are bound 
solely by electrostatic forces. If however, as in the material according to the 
invention, a substituent is also present in the divalent form in a defined 
proportion, it is conceivable that the anions in these domains (if the a- 
structure is present) may be bound in the same way as in basic salts, i.e. 
linked directly to the main layer. As a result, anisotropic lattice defects are 
induced (i.a. layer shifts) which may have positive effects on the activity of 



STA 154-FC 



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the material. Even when an electrochemical load is applied, lattice defects in 
the starting structure and hence the activity of the material remain intact over 
a relatively long period. 

2. It is also possible that, if the material is used as an electrode material in the 
5 electrode, Co(II) ions, e.g., which are present in the edge regions, may 

develop a kind of cobalt coating on the particle surface by way of a solution- 
recrystallisation process which, apart from the above-mentioned 
considerations, may explain the improvement in the electrochemical 
properties by an increase in the electronic conductivity. 

10 The proportion of Ni in the nickel mixed hydroxide according to the invention is 
preferably 60 to 92 mol %, more preferably 65 to 85 mol % and particularly 
preferably 75 to 80 mol %. In other words, the total proportion of the elements Ma, 
Mb and Mc is preferably 40 to 8 mol %, more preferably 35 to 15 mol % and 
particularly preferably 25 to 20 mol %, in each case based on the total amount of Ni, 

15 Ma, Mb and Mc. 

The proportion of the mixed valent metal Ma present is preferably 10 to 40 mol %, 
more preferably 20 to 30 mol %, based on the total amount of the elements Ma, Mb 
and Mc. 

The proportion of the optionally used doping element Mc is preferably 1 to 30 mol 
20 %, based on the total amount of the elements Ma, Mb and Mc but a maximum of 5 
mol % based on the total amount of the elements Ni, Ma, Mb and Mc. 

The proportion of the trivalent elements Mb is particularly preferably more than 60 
mol %, based on the total amount of the elements Ma, Mb and Mc, 

The degree of oxidation a of the mixed valent element Ma present, defined 
25 according to the following formula (I), is preferably from 0.01 to 0.99, more 
preferably 0.1 to 0.9, most preferably 0.25 to 0.75, 

Ma^^^'^O 

a = (I), 

Ma'^^^'^+Ma^'' 



STA 154-FC 



-6- 

wherein Ma"^^""^'^ means the molar quantity of the element Ma in the higher oxidation 

state, Ma*^"-* the molar quantity of the element Ma in the lower oxidation state, and x 
a number between 1 and 3. 

The nickel mixed hydroxides according to the invention are provided suitably in 
5 powder form, the average particle size of the powder being preferably 0.5 to 1000 
\xm, particularly preferably 2 to 100 [im and particularly preferably more than 3 ^m, 
more preferably 3-15 fim. 

The invention also provides a process for the preparation of the nickel mixed 
hydroxides described above, comprising the reaction of the reaction components 

10 required to obtain the relevant mixed hydroxides in the form of water-soluble salts 
of Ni and of the elements Ma, Mb and optionally Mc in a basic, aqueous medium for 
the co-precipitation of hydroxide reaction products with the formation of a 
homogeneous suspension of said reaction products, wherein either water-soluble 
salts of the element Ma are used in different oxidation states or a water-soluble salt 

15 of the element Ma is used in the lower oxidation state and a partial oxidation is 
carried out until the desired ratio is obtained between the different oxidation states of 
the element Ma , or a water-soluble salt of the element Ma is used in the higher 
oxidation state and a partial reduction is carried out until the desired ratio is obtained 
between the different oxidation states of the element Ma, separation from the mother 

20 liquor, washing and drying of the reaction products. 

The mixed hydroxides according to the invention may be prepared both in spherical 
and regular (non-spherical) morphology, the reaction in the first case being carried 
out advantageously in the presence of ammonia or ammonium salts. 

The reaction must be carried out under basic conditions, preferably at a pH from 8 to 
25 13. 

If a partial oxidation of the element Ma is carried out, oxidising agents known for 
such applications may be used, oxygen, H2O2, hypochlorite or peroxodisulfates 
being used in preference. The partial oxidation may be carried out advantageously 



STA 154-FC 



-7- 

by a controlled introduction of oxygen into the suspension forming. Generally 
speaking, a less than stoichiometric use of oxidising agents is suitable for partial 
oxidation. The desired ratio between the different oxidation states of the element Ma 
may be controlled by varying the oxygen supply (for example, by mixing in pure 
5 oxygen to influence the oxygen partial pressure), the reaction temperature and/or the 
pH value. 

In the case of Co, for example, a partial oxidation is achieved in an advantageous 
manner by the controlled use of atmospheric oxygen. 

In the case of Fe, for example, water-soluble salts of both oxidation states may be 
10 used simultaneously. 

If a partial reduction of the element Ma is carried out, reducing agents known for 
such applications may be used. 

If the process is carried out batchwise (batch process), it is expedient, after co- 
precipitation has ended, to carry out an ageing over several hours, for example, 1 5 to 
15 20 hours, before further work up. 

If the process is carried out continuously, the residence time is adjusted 
advantageously such that the desired mixed valent state of element Ma is obtained. 
Average residence times of several hours, for example, 5 hours, have proved to be 
advantageous. 

20 According to a further preferred process, the mixed nickel hydroxides according to 
the invention are prepared by anodic oxidation of at least one of the metal elements, 
particularly preferably at least the nickel component. To this end, the aqueous 
precipitation suspension is pumped round continuously between an electrolytic cell 
with nickel anode and a thermostat arranged outside the cell. In the circuit outside 

25 the electrolytic cell, the other metal components in the form of their water-soluble 
salts are added to the precipitation suspension, as well as alkali hydroxide, 
preferably sodium hydroxide, to adjust the pH. Moreover, the oxidising agent, 
preferably atmospheric oxygen, is introduced into the pumping circuit in order to 



STA 154-FC 



-8- 

adjust the degree of oxidation of the Ma element. Precipitation suspension is 
discharged continuously or periodically by means of an overflow, precipitation 
product is filtered, washed, dried and optionally ground. 

The anions incorporated in the precipitation product to ensure electroneutrality may 
3 then be exchanged for the preferred CO3 anions by treating the precipitation product 
in an alkali carbonate or alkali hydrogen carbonate solution, preferably NaaCOa 
solution. 

A device for the electrolytic preparation of nickel mixed hydroxide is shown 
schematically in Fig. 6. 

10 Figure 6 shows an electrolytic cell 1 which contains two cathodes 2 and an anode 3. 
The electrol5^ic brine is pumped in the base of the cell 1 via the pump 4, the heat 
exchanger 5 and the pH sensor 6. Depending on the pH measurement 6, alkali 
hydroxide or hydrochloric acid is metered into the pumping circuit as indicated by 
arrow 7. Nickel hydroxide suspension is discharged from the pumping circuit by 

15 means of pump 9 and fed to the solids separating device 10. As shown by arrow 12, 
the solids are discharged. The brine from which solids have been removed may be 
recycled by means of pump 1 1 to the pumping circuit via electrolyte work up 1 6, 
optionally with the addition of water 15. Moreover, as indicated by arrow 17, a 
means is provided for introducing the oxidising agent. Moreover, doping salt 

20 solutions are fed into the pumping circuit by means of inlet 8. According to a 
preferred embodiment, the separating device 10 is designed in the form of a screen- 
type centrifuge which is operated in such a way that fine-particle nickel hydroxide 
particles are recycled with the filtrate to the pumping circuit via pump 1 1 . Hydrogen 
gas generated during electrolysis is drawn off above the filling volume of the cell, as 

25 indicated by arrow 13. 



STA i54-FC 



-9- 



In the drawings. 

Fig. 1 shows the cycle behaviour of the sample A obtained in the examples and of 
comparison samples E, F, N and V in the half-cell test; 

Fig. 2 shows the charge curve of sample A in the 10th cycle; 

5 Fig. 3 shows the discharge curve of sample A in the 10th cycle; and 

Fig. 4 shows the x-ray diffraction spectrum of sample A. 

The nickel mixed hydroxide according to the invention is used preferably as a 
constituent of cathode materials in alkaline batteries, as in Ni/Cd or Ni/MH batteries, 
together with activators and auxiliaries known to the expert in the art. 

1 0 The invention is explained in more detail on the basis of the examples below. 



STA 154-FC 



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A) Preparation of various nickel mixed hydroxides 
Example 1 

Sample A: (3:1 Ni.dop., 3:1 Al:Co) Nio.ysAlo i88Coo.o63(OH)2 *m CO3 *nH20 

0. 1 mol of Ni(N03)2*6H20 are dissolved in 200 ml of H2O with 0.025 mol of 
5 A1(N03)3*9H20 and 0.0083 mol of Co(N03)2*6H20 and, with vigorous stirring 

(speed 400 rpm) to promote an increased introduction of atmospheric oxygen, 
metered into a charge of 0.02 mol of NaaCOs + NaOH in 500 ml of water (pH = 
12.5; 75°C) over a period of 2 h. During precipitation and the post-reaction time 
(about 3 h), the pH and temperature are kept constant. After an ageing period (with 
10 stirring) of about 18 h, the suspension is filtered over a pressure filter and washed to 
a neutral pH with water. The product mixture is then diluted to 750 ml and spray- 
dried. 

Example 2 

Sample B: (3:1 Ni:dop., 3:1 Al:Co) Nio.75Alo i88Coo.o63(OH)2 *m CO3 *nH20 

15 10 mol of NiS04*7H20, 1.25 mol of Al2(S04)3*16 H2O and 0.83 mol of 
CoS04*7H20 are dissolved in 9 1 H2O. The solution is adjusted with H2SO4 to pH = 

1, heated to 75 °C and, with vigorous stirring (400 rpm) to promote an increased 
introduction of atmospheric oxygen, metered into a charge of 15.58 mol of Na2S03 
+ NaOH in 25 1 of water (pH = 12.5; 65 - 70°C) (t = 70 min). During precipitation 

20 and the post-reaction time (about 2 h) the pH and temperature are kept constant. 
After an ageing period (with stirring) of about 16 h, the suspension is filtered over a 
membrane filter press and pressed, then dried at 50°C in a circulating air drying 
cabinet. The ground intermediate product is washed on a suction filter in portions 
with water, sodium hydroxide solution at pH = 12.5 and then again with water and 

25 dried at 50°C in a vacuum drying cabinet until a constant weight is obtained. 



STA 154-FC 



Example 3 

Sample C 

Composition as for sample B, but continuous process. 

Batch size: 180 mol (incl. 6 x preliminary run) 

5 Reactor volume: 28 1 

Average residence time: 5 h 

Volumetric flow: 5.2 1/h 

Substance flow: 2 molTh based on Ni'^"^ 

pH: 12.5 
10 Temperature: 75 °C 

Equalising alkali: NaOH, 7 mol/1 

Carbonate stream: 1.321 mol/h 

The collected reaction suspension is filtered over a membrane filter press after an 
ageing period of about 18 h (with stirring), pressed and then dried at 50°C in a 
1 5 circulating air drying cabinet. The (ground) intermediate product is re-suspended in 
water and filtered again over a membrane filter press and washed. The washed 
product is dried at 50°C in a circulating air drying cabinet until a constant weight is 
obtained. 



The analytical results of the samples A to C prepared according to the above 
20 examples are summarised in table 1 below. 



STA 154-FC 



- 12 - 



Table 1 Analysis of samples A-C 



Example 


Ni 

(wt.%) 


Al 

(wt.%) 


Co(n) 

(wt.%) 


Co(III) 
(wt.%) 


CO3 
(wt.%) 


SO4 
(ppm) 


NO3 
(ppm) 


Loss on 
drying 
105°C/2h 
(wt.%) 


Sample A 


38.80 


3.4 


4.8 


1.5 


10.5 




<2000 


5.2 


Sample B 


39.55 


4.62 


3.31 


1.4 


9.1 


6350 


<4 


4.94 


Sample C 


40.09 


4.7 


3.55 


1.6 


8.4 


6800 




2.20 



Example 4 

5 Sample D: (3.32:1 Ni/Mg:dop., 3:1 AI:Co) Nio 69Mgo o74Alo.n4Cooo58(OH)2*mC03 
*nH20 

0.1 mol of Ni(N03)2*6H20 are dissolved in 100 ml of H2O with 0.0107 mol of 
Mg(N03)2*6H20 and 0.025 mol of A1(N03)3*9H20 + 0.0083 mol of 
Co(N03)2*6H20 and, with vigorous stirring (speed 400 rpm) to promote an 

10 increased introduction of atmospheric oxygen, metered into a charge (75°C) of 0.02 
mol of K2CO3 + KOH in 150 ml of water (pH = 12.5) (t = 10 min). During 
precipitation and the post-reaction time (about 3 h), the pH and temperature are kept 
constant. After an ageing period (with stirring) of about 15 h, the suspension is 
filtered over a pressure filter and washed to a neutral pH with water. The product is 

1 5 then dried under vacuum at 50°C until a constant weight is obtained. 

Comparison example 1 

Comparison sample E: (3:1 Nirdop., 3:1 AI:Co) Nio.75Alo.,88Coo.o63(OH)2*mC03 
*nH20 

0.1 mol of Ni(S04)*7H20, 0.0125 mol of Al2(S04)3*6H20 and 0.0083 mol of 
20 Co(S04)*7H20 are dissolved in 100 ml of H2O (introduction of N2) and, with 
vigorous stirring (400 rpm), metered into a charge (75°C under an N2 atmosphere) of 
0.245 mol of Na2C03 and NaOH in 200 ml of water (pH = 12.5). During 



STA 154-FC 



- 13 - 

precipitation and the post-reaction time (about 2.5 h) the pH and temperature are 
kept constant. After an ageing period (with stirring) of about 18 h, the suspension is 
filtered over a pressure filter and washed to a neutral pH with water, then dried at 
50°C until a constant weight is obtained. 

5 Cobalt is present in the divalent form as well as Al(III), corresponding to a material 
according to the prior art according to EP 793 285. 

Comparison example 2 

Comparison sample F: (3:1 Ni:dop., 3:1 Al:Co) NiojsAlo i88Coo.o63(OH)20.188 NO3 
*nH20 

10 0.1 mol of Ni(N03)2*6H20, 0.025 mol of A1(N03)3*9H20 and 0.0083 mol of 
Co(N03)2*6H20 are dissolved in 200 ml of H2O with 0.15 mol of hexamethylene 
tetramine and adjusted to pH 4. The solution is heated slowly to boiling point, with 
vigorous stirring (400 rpra) and fiirther hexamethylene tetramine is added in 0.075 
mol portions (dissolved in 30 ml of water) until a sample of the supernatant solution 

15 exhibits no further precipitation with hexamethylene tetramine. After an ageing 
period of about 96 h, the suspension is filtered over a pressure filter, washed with 
water to a neutral pH and dried. Yield: 10.4 g (69.5%). 

The preparation took place with the use of hexamethylene tetramine under reducing 
conditions. Reducing conditions are also present in the cathodic deposition process 
20 which is used in the case of materials according to the prior art according to EP 793 
285. 

Example 5 

Sample G: (3:1 Ni:dop., 3:1 Al:Co) Nio.75Alo.i88Coo.o63(OH)2*mS04*nH20 

0.1 mol of Ni(S04)*7H20 are dissolved in 100 ml of H2O with 0.0125 mol of 
25 Al2(S04)3*6H20 and 0.0083 mol of Co(SO)4*7H20 and, with vigorous stirring (400 
rpm) to promote a high introduction of atmospheric oxygen, metered into a charge 
(75°C) of NaOH in 150 ml of water (pH = 12.5) (t = 10 min). During precipitation 



STA 154-FC 



- 14- 

and the post-reaction time (about 15 h) the pH and temperature are kept constant. 
After an ageing period (with stirring) of about 17 h, the suspension is filtered over a 
pressure filter and washed to a neutral pH with water. The product is then dried 
under vacuum at 50°C until a constant weight is obtained. 

5 The preparation took place without carbonate and thus leads to the incorporation of 
sulfate instead of carbonate ions in the intermediate layer. A subsequent partial 
carbonation by admission of air (CO2) was permitted. 

Example 6 

Sample H: (2:1 Ni:dop., 3:1 Al:Co) Nio.66Alo.248Coo.o825(OH)2*mC03*nH20 

10 0.1 mol of Ni(N03)2*6H20 are dissolved in 100 ml of H2O with 0.0375 mol of 
A1(N03)3*9H20 and 0.0125 mol of Co(N03)2*6H20 and, with vigorous stirring 
(400 rpm), introduced dropwise into a charge (75°C) of 0.02 mol of NaiCOa + KOH 
in 150 ml of water (pH == 12.5) (t = 3 h). During precipitation and the post-reaction 
time (about 4 h), the pH and temperature are kept constant. After an ageing period 

15 (with stirring) of about 15 h, the suspension is filtered over a pressure filter and 
washed to a neutral pH with water, during which process the suspension should 
never be filtered completely to dryness. The product mixture is then dried at 
50°C/200 mbar until a constant weight is obtained. 

Example 7 

20 Sample I: (11:1 Ni:dop., 2:1 Al:Co; (superlattice 33.2:1)) 

0.165 mol of Ni(N03)2*6H20 are dissolved in 400 ml of H2O with 0.01 mol of 
A1(N03)3*9H20 and 0.005 mol of Co(N03)2*6H20. With vigorous stirring (400 
rpm) and the introduction of atmospheric oxygen over a frit, the solution is metered 
into a charge of 0.04 mol of Na2N03 +NaOH in 1000 ml of H2O (pH = 12.5", 75°C) 
25 (t = 3 h). During precipitation and the post-reaction time (with stirring) of about 18 
h, the suspension is filtered over a pressure filter and washed to a neutral pH with 
water; the product mixture is then diluted to 1500 ml and then spray-dried. 



STA 154-FC 



- 15 - 

Example 8 

Sample J: (3:1 Ni:dop., 2:1 Al:Co; (superlattice 9:2:1)) 

0.09 mol of Ni(N03)2*6H20, 0.02 mol of A1(N03)3*9H20 and 0.01 mol of 
Co(N03)2*6H20 are dissolved in 200 ml of H2O and, with the introduction of an 
5 oxygen/air mixture, introduced into a charge of 0.02 mol of Na2C03 and NaOH in 
500 ml of water (pH = 12.5; 75°C) over a period of 2 h. During precipitation and the 
post-reaction time (about 3 h), the pH and temperature are kept constant. After 1 8 h 
ageing (with stirring), the suspension is filtered over a pressure filter, washed to a 
neutral pH and dried in a vacuum drying cabinet at 50°C. 

10 Example 9 

Sample K (3:1 Ni:dop., 2:1 Al:Fe) 

0.09 mol of Ni(N03)2*6H20 and 0.02 mol of Al(N03)3*9H20 are dissolved with 
0.0033 mol of Fe(N03)2*6H20 and 0.0066 mol of Fe(N03)3*6H20 and metered, 
with stirring, into a charge (35°C) of 0.02 mol of NaaCOa + NaOH in 500 ml of 
15 water (pH = 12.5) (t = 2h). During precipitation and the post-reaction time (about 3 
h), the pH and temperature are kept constant. After an ageing period of 18 h (with 
stirring), the suspension is filtered over a pressure filter, washed to a neutral pH and 
dried in a vacuum drying cabinet at 50°C. All the steps are carried out under a 
nitrogen atmosphere. 



STA 154-FC 



- 16- 



Example IQ 

Sample L: (2.9:1 Ni: dop., 3:1 Al:Co) 

800 ml/h of an electrolyte solution having the composition 63.5 g/1 of NaCI, 7.6 g/1 
of C0CI2 and 23.4 g/1 of AICI3 were pumped continuously at 8 into a test electrolytic 
5 cell 1 with a capacity of 3 1 (according to Fig.6, but without brine recycling), which 
is fitted with two Ni cathodes 2 and an Ni anode 3. Electrolysis was carried out at a 
current density of about 65 mA/cm^ (I = 30 A), at a temperature of 20°C (thermostat 
5) with anodic Ni dissolution of about 32.8 g/h. The pH was kept at 12.0 (pH 
measurement 6) during electrolysis by the automatic addition 7 of 2.5 molar sodium 

10 hydroxide solution. The electrolyte solution was pumped by means of pump 4. 

Oxygen was injected into the pumping circuit at 11. Electrolysis took place 
throughout the period in a stable manner at a voltage of about 3V. The overflow was 
drawn off by means of pump 9 and filtered by suction at 10. The sohd 12 obtained 
was dried in a circulating air drying cabinet at a temperature of 60°C. The dried 

15 material was ground (<500 \i) using a laboratory mill and carbonated in a 1 molar 
Na2C03 solution in a ratio to the dry material of 5:1 for about 2 hours at 70°C, with 
stirring, in a glass beaker. The suspension containing the product was then filtered 
by suction and the resulting solid on the filter was washed with about 8 1 of a hot 
(about 65°C) 1 g/1 sodium hydroxide solution. The product was then dried in a 

20 circulating air drying cabinet at a temperature of 60°C. Yield: 80.3 g of nickel 
hydroxide material per hour. 

The chemical analysis of the product gives the following composition: 



Ni 



40.4 wt.% 



Al 



4.87 wt.% 



25 



Co, total 



3.52 wt.% (1.7 wt.% Co^^ 



CO3 



6.47 wt.% 



CI 



<50 



ppm 



STA 154-FC 



- 17- 



10 



SO4 <50 ppm 

Na 325 ppm. 

The average particle size (Mastersizer D50) was 16 jim, the BET surface 3.3 m^/g, 
the density (He pyknometer) 2.51 g/cm^ and the tap density 1.6 g/cml 



Example 11 

Sample M: (4.5:1 Ni:dop., 3:1 Al:Co) 

Electrolysis was carried out in the same way as in example 10. The electrolyte 
solution fed in had a composition of 57.4 g/1 of NaCl, 4.56 g/1 of CoC]2 and 14.01 
g/1 of AICI3. The pH was kept at 12.5. The voltage was 3.2V; the anodic Ni 
dissolution was 29.5 g/h. 



The overflow from the electrolytic cell was collected over 6 hours, left to stand for 
about 20 hours to age and then filtered by suction. The resulting solid was washed 
on the suction filter with about 3.8 1 of a 1 g/1 sodium hydroxide solution, then with 
15 about 1.9 1 of a 1 molar Na2C03 solution and then again with about 3.8 1 of a 1 g/1 
sodium hydroxide solution. The temperature of the wash solutions was about 20°C. 
The product was then dried in a circulating air drying cabinet at a temperature of 
about 60°C. The dried material was ground using a laboratory mill (<500 fx) and 
then analysed. Yield: 453 g of nickel hydroxide material. 

20 The chemical analysis gave the following composition: 

Ni 43.4 wt.% 

Al 3.33 wt.% 

Co, total 2.42 wt.% (1.12 wt.% Co^"^ 

CO3 9.09 wt.% 

25 CI 510 ppm 

SO4 <50 ppm 



STA 154-FC 



- IS 



Na 0.83 ppm. 

The average particle size (Mastersizer D50) was 38 [im, the BET surface <1 m^/g, 
the physical density (He pyknometer) 2.45 g/cm^ and the tap density 1.6 g/cm^ and 
the loss on drying (105°C, 2h) was 4.75 wt.%. 

5 Example 12 

Sample N: (4:1 Ni:dop., 3:1 Al:Co) 

An electrolytic cell with a capacity of 400 1 was used. Electrolysis was carried out in 
a similar way to example 10. 55 17h of an electrolyte solution having the composition 
52.7 g/1 of NaCl, 5.5 g/1 of C0CI2 and 17.0 g/1 AICI3 were added. The electrolysis 

10 current was 2000 A with an anode current density of 69 mA/cm^. The Ni dissolution 
was 2187 g/h, the pH 12.0. After a preliminary run time of about 20 h, the 
outflowing suspension was collected for 28 hours. This 28-hour collection sample 
(1648 1) was then filtered by suction and the resulting solid dried in a circulating air 
drying cabinet at a temperature of 70 to 80°C. The dried material was ground (<1000 

15 ^im) using a conical grinder and carbonated with a 1 molar Na2C03 solution in a 
ratio to the dry material of 5:1 for about 2 hours at 70°C, with stirring, in a 450 1 
reactor. The suspension was then filtered by suction and the resulting solid was 
washed on the suction filter with about 2.5 of a hot (about 65°C) 1 g/1 sodium 
hydroxide solution. The product was then dried in a circulating air drying cabinet at 

20 a temperature of 70 to 80°C. 

The chemical analysis gave the following composition of the product: 

Ni 44.40 wt.% 

Al 3.75 wt.% 

Co, total 2.82 wt.% (2.0 wt.% Co^^) 

25 CO3 8.33 wt.% 

CI 360 ppm 

SO4 <50 ppm 



STA 154-FC 



- 19- 

Na 270 ppm. 

The average particle size (Mastersizer D50) was 51.8 |am, the BET surface 6.35 
vc?lg, the physical density (He pyknometer) 2.7 g/cm^ and the tap density 1.8 g/cm^. 
Fig 7 shows an SEM photo of the powder. 

5 B) Electrochemical characterisation 

In order to obtain an electrochemical characterisation of the samples, 
charging/discharge cycles were carried out with a five-hour charging and discharge 
current in 30% KOH against Hg/HgO with a charging factor of 1.5. The electrode 
material of nickel mixed hydroxide (active material), 33% graphite as conductive 
10 additive and hydroxypropylmethylcellulose as binder was pasted into nickel foam as 
substrate. 

Figure 1 shows the cycle behaviour of samples A and N and of comparison samples 
E and F according to the prior art (EP 0 793 285) and of comparison sample V, a 
Co(III), Mn(III) and Al(III)-containing nickel hydroxide powder according to EP 0 
15 7 1 2 1 74 in the half-cell test. 

Comparison samples E and F according to EP 0 793 285 contain divalent cobalt in 
addition to trivalent other additional cations since divalent cobalt e.g. in combination 
with trivalent aluminium is used as starting compounds and also no oxidising agent 
is used. No details about cycle behaviour and capacity values can be derived from 
20 EP 0 793 285 so comparison samples were prepared: samples E and F were prepared 
maintaining the divalency for cobalt, once under an N2 atmosphere (E) and once 
under reducing conditions (F), and compared as prior art with sample A according to 
the invention. 

As Figure 1 shows, both the capacity values and the cycle behaviour of samples A 
25 and N in which Co(lII) as well as Co(n) ions are present are markedly superior to 
the materials according to the prior art in which the cobalt ions are present only in 
the divalent form. The positive influence of the mixed valency for cobalt becomes 
particularly pronounced by a comparison with sample E which was prepared not 



STA 154-FC 



-20- 

\inder reducing conditions but only with the exclusion of oxygen. Slight partial 
oxidation of the surface during work up is conceivable here, which could explain the 
improvement compared with the material prepared under reducing conditions 
(sample F). Samples A and N also exhibit marked improvements in terms of 
5 capacity and cycle stability compared with comparison sample V. 

The potential curve of sample A is shown in Figures 2 and 3, Figure 2 showing the 
charging curve and Figure 3 showing the discharge curve in the 1 0th cycle, in each 
case against Hg/HgO. 

The X-ray diffraction spectrum of sample A is shown in Figure 4. The material of 
10 sample A shows the reflections of the hydrotalcite type with a distance of about 7.8 
A between the layers. In contrast to P-Ni(OH)2 (brucite type), an expanded layer 
structure is present. Figure 5 shows the X-ray diffraction spectrum of sample L. 



STA 154-FC 



-21 - 

Patent claims 

1. Nickel mixed hydroxide with Ni as the main element and with a layer 
structure, comprising 

a) at least one element Ma from the group comprising Fe, Cr, Co, Ti, Zr 
and Cu which is present in two different oxidation states which differ 
by one electron in terms of the number of outer electrons; 

b) at least one element Mb from the group comprising B, Al, Ga, In and 
RE (rare earth metals, preferably Sc, Y or La) present in the trivalent 
oxidation state; 

c) optionally at least one element Mc from the group comprising Mg, 
Ca, Sr, Ba and Zn present in the divalent oxidation state; 

d) apart from the hydroxide, at least one additional anion from the group 
comprising halides (preferably fluoride or chloride), carbonate, 
sulfate, acetate, oxalate, borate and phosphate in a quantity sufficient 
to preserve the electroneutrality of the mixed hydroxide; and 

e) water of hydration in a quantity which stabilises the relevant structure 
of the mixed hydroxide, 

2. Nickel mixed hydroxide according to claim 1, wherein the proportion of Ni 
is 60 to 92 mol %, preferably 65 to 85 mol %, more preferably 75 to 80 mol 
% and the total proportion of the elements Mg, Mb and Mc is 40 to 8 mol %, 
preferably 35 to 15 mol %, more preferably 25 to 20 mol %, in each case 
based on the total amount of Ni, Ma, Mb and Mc. 

3. Nickel mixed hydroxide according to claim 1 and/or claim 2, wherein the 
proportion of the element Ma is 10 to 40 mol %, preferably 20 to 30 mol %, 
based on the total amount of the elements Ma, Mb and Mc. 



154-FC 



-22- 

Nickel mixed hydroxides according to at least one of claims 1 to 3, wherein 
the proportion of the element Mc is 1 to 30 mol %, based on the total amoxmt 
of elements Ma, Mb and Mc. 

Nickel mixed hydroxide according to at least one of claims 1 to 4, wherein 
the degree of oxidation a of the element Ma, defined according to the 
following formula (I), is from 0.01 to 0.99, preferably 0.1 to 0.9, more 
preferably 0.25 to 0.75: 
Ma^^""') 

a= (I), 

Ma'^'^'^^+Ma"'' 

wherein Ma"^*^"*'^ means the molar quantity of the element Ma in the higher 
oxidation state, and Mg the molar quantity of the element Ma in the lower 
oxidation state, and x is a number between 1 and 3. 

Nickel mixed hydroxide according to at least one of claims 1 to 5 in the form 
of a powder with an average particle size from 1 to 100 \im. 

Process for the preparation of the nickel mixed hydroxides according to any 
one of claims 1 to 6, comprising the reaction of the reaction components 
required to obtain the relevant mixed hydroxides in the form of water-soluble 
salts of Ni and of the elements Ma, Mb and optionally Mc in a basic, aqueous 
medium for the co-precipitation of hydroxide reaction products with the 
formation of a homogeneous suspension of said reaction products, wherein 
either water-soluble salts of the element Ma are used in different oxidation 
states or a water-soluble salt of the element Ma is used in the lower oxidation 
state and a partial oxidation is carried out until the desired ratio is obtained 
between the different oxidation states of the element Ma, or a water-soluble 
salt of the element Ma is used in the higher oxidation state and a partial 
reduction is carried out until the desired ratio is obtained between the 
different oxidation states of the element Ma, separation of the water from the 
suspension, and drying of the reaction products. 



STA 154-FC 



-23- 



8. Process according to claim 7, wherein at least one of the reaction components 
is introduced into the aqueous medium by anodic oxidation of the 
corresponding metal. 

9. Process according to claim 7 or 8, wherein the reaction is carried out at a pH 
5 from 8 to 13. 

10. Process according to any one of claims 7 to 9, wherein partial oxidation is 
carried out by using oxygen, H2O2, hypochlorite, peroxodisulfates or 
percarbonates as oxidising agent. 



11. 

10 



Use of the nickel mixed hydroxides according to any one of claims 1 to 6 as 
cathode material in alkaline batteries. 



STA154-FC 



-24- 

Nickel mixed hydroxide, process for the preparation thereof and use thereof as 
cathode material in alkaline batteries 

Abstract 

The invention describes a nickel mixed hydroxide with Ni as the main element and 
witli a layer structure, comprising at least one element Ma from the group 
comprising Fe, Cr, Co, Ti, Zr and Cu which is present in two different oxidation 
states which differ by one electron in terms of the number of outer electrons; at least 
one element Mb from the group comprising B, Al, Ga, hi and RE (rare earth metals) 
present in the trivalent oxidation state; optionally at least one element Mc from the 
group comprising Mg, Ca, Sr, Ba and Zn present in the divalent oxidation state; 
apart from the hydroxide, at least one additional anion from the group comprising 
halides, carbonate, sulfate, oxalate, acetate, borate and phosphate in a quantity 
sufficient to preserve the electroneutrality of the mixed hydroxide; and water of 
hydration in a quantity which stabilises the relevant structure of the mixed 
hydroxide. 

The preparation of the nickel mixed hydroxide according to the invention is carried 
out by co-precipitation of the hydroxides in an alkaline medium. The nickel mixed 
hydroxides according to the invention are characterised by very high electrochemical 
utilisation of the nickel ions and high mass-related capacity values with very good 
cycle stability and are therefore advantageously suitable as cathode material in 
alkaline batteries. 



863995 




Fig 2 

550 1 
500- 
450 
400 
350 
300 
250 
200 
150 
100 
50 
0 



o 



c 

<1; 
C7) 



"c 







































522,1 





































































































































































































































mAh/g 



X 

c 

Of 
C7» 

0; 

> 
E 



c 



• g. 3 

500 
A50 
400 
350 
300 
250 
200 
150 
100 
50 



0 

-300 



-250 



-200 



-150 
mAh/g 



-100 



-50 



Fig. /» 

2-ThGta-Scala 
80.00| ^ > ^ 




ig 6 

13 




868995 



Fig 7 




00008295 1;jm HOST 




COMBINED DECLARATION AND POWER OF ATTORNEY 



ATTORNEY DOCKET NO 



As a below named inventor, I hereby declare that: 

My residence, post office address and citizenship are as stated below next to my 
name. I believe I am the original, first and sole inventor (if only one name is 
listed below) or an original, first and joint inventor (if plural names are list- 
ed below) of the subject matter which is claimed and for which a patent is 
sought 

on the invention entitled 

"NICKEL MIXED HYDROXIDE, METHOD FOR THE PRODUCING THE SAME, AND 
THE USE THEREOF AS A CATHODE MATERIAL IN ALKALINE BATTERIES" 

the specification of which is attached hereto, 

or was filed on December 14, 1999 

as a POT AppUcation Serial No. PCT/EP99/09912 

I hereby state that I have reviewed and understand the contents of the above - 
identified specification, including the claims. 

I acknowledge the duty to disclose information which is material to the patent- 
ability of this appUcation in accordance with Title 37, Code of Federal Regula- 
tions, §1.56. 

I hereby claim foreign priority benefits under Title 35, United States Code, §119 
of any foreign application(s) for patent or inventor's certificate listed below 
and have also identified below any foreign application for patent or inventor's 
certificate having a filing date before that of the application on which priority 
is claimed: 

Prior Foreign Application (s ) , the priority(ies) of which is/are to be claimed: 

198 60 143.3 Germany December 24, 1998 
(Number) (Country) (Month/ Day /Year Filed) 

199 39 025.8 Germany August 18, 1999 
(Number) (Country) (Month/ Day /Year Filed) 

I hereby claim the benefit under Title 35, United States Code, §120 of any Unit- 
ed States application (s) hsted below and, insofar as the subject matter of each 
of the claims of this application is not disclosed in the prior United States 
appUcation in the manner provided by the first paragraph of Title 35, United 
States Code, §112, I acknowledge the duty to disclose the material information as 
defined in Title 37, Code of Federal Regulations, §1.56 which occured between 
the filing date of the prior application and the national or PCT international 
filing date of this application: 



(Application Serial No.) (Filing Date) (Status) 

(patented, pending, abandoned) 

(AppUcation Serial No.) (Filing Date) ~ (Status) 

(patented, pending, abandoned) 

I hereby declare that aU statements made herein of my own knowledge are 
true and that aU statements made on information and beUef are beUeved to be 
true; and further that these statements were made with the knowledge that wiU- 
ful false statements and the Uke so made are punishable by fine or imprisonment, 
or both, under Section 1001 of Title 18 of the United States Code and that such 
willful false statements may jeopardize the validity of the appUcation or any 
patent issued thereon. 



STA 154-US 



POWER OF ATTORNEY: As a named inventor, I hereby appoint the following attomey(s) and/or agent(s) to prosecute 
this application and to transact all business in the Patent and Trademark OiUce connected therewith: 



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[ ^ N. DENISE BROWN, Patent Office Registration Numbeiv2fi4S2I_ 
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DIDERICO VAN EYL, Patent Office Registration Number 38^641^ 
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