Process for making a nickel composite hydroxide

Abstract

Described herein is a process for making a nickel composite hydroxide with a mean particle diameter d50 in the range from 3 to 20 ?m including combining (a) an aqueous solution of water-soluble salts of nickel and of at least one of cobalt and manganese, and, optionally, at least one of Al, Mg, B, or transition metals other than nickel, cobalt, and manganese, (b) an aqueous solution of an alkali metal hydroxide and (c) an aqueous solution of alkali metal (bi)carbonate or ammonium (bi)carbonate in the molar ratio of 0.001:1 to 0.04:1, and, optionally, (d) an aqueous solution of alkali metal aluminate,
in a continuous stirred tank reactor or in a cascade of at least two continuous stirred tank reactors.

Claims

1. A nickel composite hydroxide in particulate form with a mean particle diameter d50 in the range from 3 to 20 ?m and a width of particle diameter distribution, calculated as [(d90?d10)/(d50)], of at least 0.61, containing in the range of from 60 to 95 mole-% Ni and at least one transition metal selected from the group consisting of Co and Mn, and in the range of from 0.1 to 3.0% by weight of carbonate, with respect to said nickel composite hydroxide.

2. The nickel composite hydroxide according to claim 1 having a composition according to general formula (II)
(Ni.sub.aCo.sub.bAl.sub.c).sub.1-d-M.sub.dO.sub.x(OH).sub.y(CO.sub.3).sub.z(II) wherein a is in the range from 0.60 to 0.95, b is in the range of from 0.025 to 0.2, c is in the range of from 0.005 to 0.1, d is in the range of from zero to 0.05, and M is selected from the group consisting of Mg, B and transition metals other than Co and Ni, and combinations of at least two of the foregoing, wherein a+b+c=1.0, 0?x<1, 1<y?2.1, and 0<z?0.25.

3. The nickel composite hydroxide according to claim 1 wherein the metal part has a composition according to general formula (III)
(Ni.sub.aCo.sub.bAl.sub.c).sub.1-d-M.sub.d(III) wherein: a is in the range from 0.80 to 0.95, b is in the range of from 0.025 to 0.195, c is in the range of from 0.02 to 0.05, d is in the range of from zero to 0.035, and M is selected from the group consisting of one or more of Ti, Zr, Nb, W, and Mg, and combinations of Mg and at least one of Ti, Zr, Nb, and W, wherein a+b+c=1.0 and b+c<0.20.

4. The nickel composite hydroxide according to claim 1 wherein said nickel composite hydroxide has a specific surface (BET) in the range of from 5 to 70 m.sup.2/g.

5. A method of using the nickel composite hydroxide according to claim 1, the method comprising using the nickel composite hydroxide as a precursor for the manufacture of cathode active materials for lithium ion batteries.

6. A process for making the nickel composite hydroxide of claim 1 comprising combining (a) an aqueous solution of water-soluble salts of nickel and of at least one of cobalt and manganese, and, optionally, at least one of Al, Mg, B, or transition metals other than nickel, cobalt, and manganese, (b) an aqueous solution of an alkali metal hydroxide, (c) an aqueous solution of alkali metal (bi)carbonate or ammonium (bi)carbonate in the molar ratio of 0.001:1 to 0.04:1, referring to alkali metal hydroxide, and, optionally, (d) an aqueous solution of alkali metal aluminate, in a continuous stirred tank reactor or in a cascade of at least two continuous stirred tank reactors in one or more steps, wherein solutions (b) and (c) are combined first followed by combination with solution (a) and optionally with solution (d), or solutions (a) and (c) are combined first followed by combination with solution (b) and optionally with solution (d), or solutions (a), (b), (c) and optionally (d) are combined simultaneously.

7. The process according to claim 6 wherein said nickel composite hydroxide contains a combination of transition metals and further metals according to general formula (I)
(Ni.sub.aCo.sub.bAl.sub.c).sub.1-dM.sub.d(I) wherein a is in the range from 0.70 to 0.95, b is in the range of from 0.025 to 0.2, c is in the range of from 0.005 to 0.1, d is in the range of from zero to 0.05, and M is selected from the group consisting of Mg, B and transition metals other than Co and Ni, and combinations of at least two of the foregoing, wherein a+b+c=1.0.

8. The process according to claim 6, wherein said process is carried out a pH value in the range of from 11.5 to 12.8.

9. The process according to claim 6, wherein said process is carried out in a cascade of at least two continuous stirred tank reactors, and wherein (a) is combined with (b) and (c) in the first tank reactor at a pH value in the range of from 12.0 to 12.8 and in the second tank reactor at a pH value in the range of from 11.5 to 12.4.

10. The process according to claim 7, wherein M includes Mg in the range of from 0.1 to 2.5 mole-% with respect to the metals in said nickel composite hydroxide.

11. The process according to claim 6, wherein the water-soluble salts are selected from the group consisting of sulfates and nitrates.

12. The process according to claim 6, wherein said process includes the addition of a solution (d) comprising alkali metal aluminate.

Description

EXAMPLE 1

(1) The following solutions were made: Solution (a.1): aqueous solution of NiSO.sub.4 and CoSO.sub.4 (molar ratio Ni:Co of 19:1) with a total metal concentration of 1.63 mol/kg Solution (b.1): aqueous solution of NaOH, 25% by weight Solution (c.1): aqueous solution of Na.sub.2CO.sub.3, 5% by weight Solution (d.1): 10% by weight aqueous solution of NaAlO.sub.2 in water Ammonia solution: 25% By weight aqueous NH.sub.3 solution

(2) Solution (b.1) and (c.1) were mixed so that the molar ratio of carbonate to hydroxide was 0.002.

(3) A 46-l stirred tank reactor with overflow system was charged with aqueous 3% by weight ammonium sulfate solution. The temperature in the tank reactor was set to 60? C. while the ammonium sulfate solution was stirred. Nitrogen gas flow was introduced into the reactor to decrease oxygen content in the reaction volume below 2%.

(4) Solution (a.1) was introduced to the reactor at a rate of 8.6 kg/h. Simultaneously, solution (d.1), the ammonia solution and the combined solutions (b.1) and (c.1) were introduced through separate feeds into the reactor at rates of 0.135 kg/h, 0.39 kg/h and 3.2 kg/h, respectively. The flow rate of the combined solutions (b.1) and (c.1) was adjusted by a pH regulation circuit to keep the pH value in the range of 12.2?0.1.

(5) Throughout the process, reaction temperature was maintained at 60? C. and the stirring speed was set to introduce about 2 W/I into reaction volume. The stirred tank reactor was operated continuously keeping the liquid level in the reactor vessel essentially constant. Inventive nickel composite hydroxide M-OH.1 with an average particle size d50 of 13.4 ?m was collected via free overflow from the stirred tank reactor and isolated by filtration.

(6) The metal content of the resultant hydroxide-OH.1 was Ni.sub.0.905Co.sub.0.475Al.sub.0.475. The variable z in the respective formula (I.1) corresponds to 0.048.

(7) M-OH.1 is mixed with LiOH in about equimolar amounts. The resulting mixture is calcined at 755? C. for 9 hours in a forced flow of oxygen-enriched air, molar ratio O.sub.2/N.sub.2 of 3:2. A cathode active material is obtained that exhibits high gravimetric capacity and high tap density.

EXAMPLE 2

(8) The following solutions were made: Solution (a.2): aqueous solution of NiSO.sub.4 and CoSO.sub.4 (molar ratio Ni:Co of 24:1) with a total metal concentration of 1.65 mol/kg Solution (b.2): mixture of aqueous solution of NaOH and aqueous solution of ammonia. The NaOH concentration and ammonia concentration in this solution were 23.7 w % and 2.7 w %, respectively. Solution (c.2): aqueous solution of Na.sub.2CO.sub.3, 0.28% by weight Solution (d.2): 5.3% by weight aqueous solution of NaAlO.sub.2 Solution (b.2) and (c.2) were mixed so that the molar ratio of carbonate to hydroxide was 0.0022.

(9) A 8-l stirred tank reactor with overflow system was charged with aqueous 3% by weight ammonium sulfate solution. The temperature in the tank reactor was set to 60? C. while the ammonium sulfate solution was stirred. Nitrogen gas flow was introduced into the reactor to decrease oxygen content in the reaction volume below 2%.

(10) Solution (a.2) was introduced to the reactor at a rate of 1128.3 g/h. Simultaneously, solutions (d.2), (b.2) and (c.2) were introduced into the reactor at rates of 197.2 g/h, 499.7 g/h and 257.2 g/h, respectively. The flow rate of the combined solutions (b.2) and (c.2) was adjusted by a pH regulation circuit to keep the pH value in the range of 12.2?0.1.

(11) Throughout the process, reaction temperature was maintained at 60? C. and the stirring speed was set to introduce about 2 W/I into reaction volume. The stirred tank reactor was operated continuously keeping the liquid level in the reactor vessel essentially constant. Inventive nickel composite hydroxide M-OH.2 with an average particle size d50 of 13.3 ?m was collected via free overflow from the stirred tank reactor and isolated by filtration.

(12) The metal content of M-OH.2 was Ni.sub.0.905Co.sub.0.375Al.sub.0.575.

(13) M-OH.2 is mixed with LiOH in about equimolar amounts. The resulting mixture is calcined at 755? C. for 9 hours in a forced flow of oxygen-enriched air, molar ratio O.sub.2/N.sub.2 of 3:2. A cathode active material is obtained that exhibits high gravimetric capacity and high tap density.

EXAMPLE 3

(14) The following solutions were made: Solution (a.3): aqueous solution of NiSO.sub.4 and CoSO.sub.4 (molar ratio Ni:Co of 24:1) with a total metal concentration of 1.65 mol/kg Solution (b.3): mixture of aqueous solution of NaOH and aqueous solution of ammonia. The NaOH concentration and ammonia concentration in this solution were 23.7 w % and 2.7 w %, respectively. Solution (c.3): aqueous solution of Na.sub.2CO.sub.3 0.28% by weight Solution (d.3): 5.3% by weight aqueous solution of NaAlO.sub.2 Solution (b.3) and (c.3) were mixed so that the molar ratio of carbonate to hydroxide was 0.0022.

(15) A 8-l stirred tank reactor with overflow system was charged with aqueous 3% by weight ammonium sulfate solution. The temperature in the tank reactor was set to 60? C. while the ammonium sulfate solution was stirred. Nitrogen gas flow was introduced into the reactor to decrease oxygen content in the reaction volume below 2%.

(16) Solution (a.3) was introduced to the reactor at a rate of 1128.3 g/h. Simultaneously, solutions (d.3), (b.3) and (c.3) were introduced into the reactor at rates of 197.2 g/h, 499.7 g/h and 257.2 g/h, respectively. The flow rate of the combined solutions (b.3) and (c.3) was adjusted by a pH regulation circuit to keep the pH value in the range of 12.5?0.1.

(17) Throughout the process, reaction temperature was maintained at 60? C. and the stirring speed was set to introduce about 2 W/I into reaction volume. The stirred tank reactor was operated continuously keeping the liquid level in the reactor vessel essentially constant. Inventive nickel composite hydroxide M-OH:3 with an average particle size d50 of 4.1 ?m was collected via free overflow from the stirred tank reactor and isolated by filtration.

(18) The metal content of M-OH.3 was Ni.sub.0.905Co.sub.0.375Al.sub.0.575.

(19) M-OH.3 is mixed with LiOH in about equimolar amounts. The resulting mixture is calcined at 755? C. for 9 hours in a forced flow of oxygen-enriched air, molar ratio O.sub.2/N.sub.2 of 3:2. A cathode active material is obtained that exhibits high gravimetric capacity and high tap density.

EXAMPLE 4

(20) The following solutions were made: Solution (a.4): aqueous solution of NiSO.sub.4 and CoSO.sub.4 (molar ratio Ni:Co of 24:1) with a total metal concentration of 1.65 mol/kg Solution (b.4): mixture of aqueous solution of NaOH and aqueous solution of ammonia. The NaOH concentration and ammonia concentration in this solution were 23.7 w % and 2.7 w %, respectively. Solution (c.4): aqueous solution of Na.sub.2CO.sub.3 0.28% by weight Solution (d.4): 5.3% by weight aqueous solution of NaAlO.sub.2 Solution (b.4) and (c.4) were mixed so that the molar ratio of carbonate to hydroxide was 0.0022.

(21) A 8-l stirred tank reactor with overflow system was charged with aqueous 3% by weight ammonium sulfate solution. The temperature in the tank reactor was set to 60? C. while the ammonium sulfate solution was stirred. Nitrogen gas flow was introduced into the reactor to decrease oxygen content in the reaction volume below 2%.

(22) Solution (a.4) was introduced to the reactor at a rate of 1128.3 g/h. Simultaneously, solutions (d.4), (b.4) and (c.4) were introduced into the reactor at rates of 197.2 g/h, 499.7 g/h and 257.2 g/h, respectively. The flow rate of the combined solutions (b.4) and (c.4) was adjusted by a pH regulation circuit to keep the pH value in the range of 12.3?0.1.

(23) Throughout the process, reaction temperature was maintained at 60? C. and the stirring speed was set to introduce about 2 W/I into reaction volume. The stirred tank reactor was operated continuously keeping the liquid level in the reactor vessel essentially constant. Inventive nickel composite hydroxide M-OH.4 with an average particle size d50 of 11 ?m was collected via free overflow from the stirred tank reactor and isolated by filtration.

(24) The metal content of M-OH.4 was Ni.sub.0.905Co.sub.0.375Al.sub.0.575.

(25) M-OH.4 is mixed with LiOH in about equimolar amounts. The resulting mixture is calcined at 755? C. for 9 hours in a forced flow of oxygen-enriched air, molar ratio O.sub.2/N.sub.2 of 3:2. A cathode active material is obtained that exhibits high gravimetric capacity and high tap density.

EXAMPLE 5

(26) The following solutions were made: Solution (a.5): aqueous solution of NiSO.sub.4 and CoSO.sub.4 (molar ratio Ni:Co of 24:1) with a total metal concentration of 1.65 mol/kg Solution (b.5): mixture of aqueous solution of NaOH and aqueous solution of ammonia. The NaOH concentration and ammonia concentration in this solution were 23.7 w % and 1.35 w %, respectively. Solution (c.5): aqueous solution of Na.sub.2CO.sub.3 0.48% by weight Solution (d.5): 5.3% by weight aqueous solution of NaAlO.sub.2 Solution (b.5) and (c.5) were mixed so that the molar ratio of carbonate to hydroxide was 0.0038.

(27) A 8-l stirred tank reactor with overflow system was charged with aqueous 1.5% by weight ammonium sulfate solution. The temperature in the tank reactor was set to 60? C. while the ammonium sulfate solution was stirred. Nitrogen gas flow was introduced into the reactor to decrease oxygen content in the reaction volume below 2%.

(28) Solution (a.5) was introduced to the reactor at a rate of 1128.3 g/h. Simultaneously, solutions (d.5), (b.5) and (c.5) were introduced into the reactor at rates of 197.2 g/h, 499.7 g/h and 257.2 g/h, respectively. The flow rate of the combined solutions (b.5) and (c.5) was adjusted by a pH regulation circuit to keep the pH value in the range of 11.8?0.1.

(29) Throughout the process, reaction temperature was maintained at 60? C. and the stirring speed was set to introduce about 2 W/I into reaction volume. The stirred tank reactor was operated continuously keeping the liquid level in the reactor vessel essentially constant. Inventive nickel composite hydroxide M-OH.5 with an average particle size d50 of 15.9 ?m was collected via free overflow from the stirred tank reactor and isolated by filtration.

(30) The metal content of M-OH.5 was Ni.sub.0.905Co.sub.0.375Al.sub.0.575.

(31) M-OH.5 is mixed with LiOH in about equimolar amounts. The resulting mixture is calcined at 755? C. for 9 hours in a forced flow of oxygen-enriched air, molar ratio O.sub.2/N.sub.2 of 3:2. A cathode active material is obtained that exhibits high gravimetric capacity and high tap density.

EXAMPLE 6

(32) The following solutions were made: Solution (a.6): aqueous solution of NiSO.sub.4 and CoSO.sub.4 (molar ratio Ni:Co of 24:1) with a total metal concentration of 1.65 mol/kg Solution (b.6): mixture of aqueous solution of NaOH and aqueous solution of ammonia. The NaOH concentration and ammonia concentration in this solution were 23.7 w % and 1.35 w %, respectively. Solution (c.6): aqueous solution of Na.sub.2CO.sub.3 0.48% by weight Solution (d.6): 5.3% by weight aqueous solution of NaAlO.sub.2 Solution (b.6) and (c.6) were mixed so that the molar ratio of carbonate to hydroxide was 0.0038.

(33) A 8-l stirred tank reactor with overflow system was charged with aqueous 1.5% by weight ammonium sulfate solution. The temperature in the tank reactor was set to 60? C. while the ammonium sulfate solution was stirred. Nitrogen gas flow was introduced into the reactor to decrease oxygen content in the reaction volume below 2%.

(34) Solution (a.6) was introduced to the reactor at a rate of 1128.3 g/h. Simultaneously, solutions (d.6), (b.6) and (c.6) were introduced into the reactor at rates of 197.2 g/h, 499.7 g/h and 257.2 g/h, respectively. The flow rate of the combined solutions (b.6) and (c.6) was adjusted by a pH regulation circuit to keep the pH value in the range of 12.0?0.1.

(35) Throughout the process, reaction temperature was maintained at 60? C. and the stirring speed was set to introduce about 2 W/I into reaction volume. The stirred tank reactor was operated continuously keeping the liquid level in the reactor vessel essentially constant. Inventive nickel composite hydroxide M-OH.6 with an average particle size d50 of 10.0 ?m was collected via free overflow from the stirred tank reactor and isolated by filtration.

(36) The metal content of M-OH.6 was Ni.sub.0.905Co.sub.0.375Al.sub.0.575.

(37) M-OH.6 is mixed with LiOH in about equimolar amounts. The resulting mixture is calcined at 755? C. for 9 hours in a forced flow of oxygen-enriched air, molar ratio O.sub.2/N.sub.2 of 3:2. A cathode active material is obtained that exhibits high gravimetric capacity and high tap density.