CN100364899C - Core-shell composite phase-structured nickel hydroxide and its preparation method and application - Google Patents
Core-shell composite phase-structured nickel hydroxide and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to core-shell composite phase-structured nickel hydroxide and a preparation method thereof and use, which relates to a battery positive electrode material, particularly to a nickel hydroxide battery positive electrode material with the core-shell composite phase structure and a preparation method thereof and use. The present invention provides a nickel hydroxide positive electrode material with the core-shell composite phase structure and a preparation method thereof, which uses spherical beta phase nickel hydroxide as a core to hold the material to have higher tap density and uses alpha-Ni (OH) 2 as a shell to make the material obtain higher mass ratio and discharge capacity and favorable cycle life and capacity storage holding capacity. The alpha phase nickel hydroxide is used as the shell, the beta phase nickel hydroxide is used as the core, and the mass ratio of the alpha phase nickel hydroxide and the beta phase nickel hydroxide is from 0.1 to 1: 1. The spherical beta phase nickel hydroxide is prepared with a controlled crystallization method, particularly the spherical beta phase nickel hydroxide which is doped with cobalt and zinc, the core of the spherical beta phase nickel hydroxide is deposited with aluminium, cobalt, manganese and yttrium to replace the shell of the stable alpha phase, and the product is obtained.
Description
Technical field
The present invention relates to a kind of cell positive material, especially relate to a kind of have core-shell composite phase-structured nickel hydroxide cell positive material and preparation method thereof and application.
Background technology
Nickel hydroxide (Ni (OH)
2) be a kind of important battery material, be widely used in the nickel series rechargeable batteries such as alkaline Ni-MH, Ni-Cd, Ni-Zn.Spherical beta phase nickel hydroxide has higher tap density, and satisfactory stability is arranged in alkaline electrolyte.But simple beta phase nickel hydroxide not only electrochemical activity is not fine, and is easy to generate the less γ phase hydroxy nickel oxide of density during charging in this higher concentration alkaline electrolyte, causes electrode to expand, and the infringement battery influences the cycle life of battery.Spherical beta phase nickel hydroxide through elements such as impurity Co, Zn has better electrochemical activation, can suppress the generation of γ phase hydroxy nickel oxide to a certain extent.Doping spherical β-the Ni (OH) that makes as Chinese patent 98123187.X
2Actual tap density can reach 2.2g/cm
3, specific discharge capacity is greater than 270mAh/g.Doping spherical β-Ni (OH)
2Now be the positive electrode material of commercialization widespread production as alkaline nickel series rechargeable battery.
(theoretical specific capacity can be up to 433mAh/g because of having higher loading capacity for class alpha-phase nickel hydroxide, be 1.5 times of beta phase nickel hydroxide approximately) (class alpha-phase nickel hydroxide and its Charging state γ hydroxy nickel oxide density mutually are more or less the same with better cycle life, be difficult for the generating electrodes expansion issues when discharging and recharging) pay close attention to widely obtaining people in recent years, and the γ phase hydroxy nickel oxide of class alpha-phase nickel hydroxide Charging state has much better stability in storage than the beta-phase nickel oxyhydroxide of beta phase nickel hydroxide Charging state in alkali lye, can reduce self-discharge, improve the battery service efficiency, this point in large vol nickel series battery highly significant.Yet simple class alpha-phase nickel hydroxide structure can not stable existence in alkaline electrolyte, and nowadays people carry out the method by the elements such as about 20%Al that mix, and can prepare the class alpha-phase nickel hydroxide that has good stability at alkali lye.But the tap density of class alpha-phase nickel hydroxide is because of its theoretical density (2.82g/cm
3) this is just lower, can not reach the tap density of spherical beta phase nickel hydroxide in actual at present preparation.As the prepared α-Ni (OH) of Chinese patent 97123054.4
2The about 1.6g/cm of tap density
3, specific discharge capacity reaches 355mAh/g.And for battery material,, not only requiring its specific discharge capacity height also to require its tap density big because of the volume of battery own limits to some extent, battery could obtain higher capacity like this.Solved the α-Ni (OH) of stability problem
2A major reason of now can't commercialization using is exactly that its tap density is lower.
Summary of the invention
The objective of the invention is to take all factors into consideration α and β Ni (OH) mutually
2Relative merits separately, providing a kind of is nuclear with spherical beta phase nickel hydroxide, keeps material to have higher tap density; With α-Ni (OH)
2Be shell, make material obtain higher quality than loading capacity, good cycle life and capacity store hold facility, have core-shell composite phase-structured nickel hydroxide anode material and preparation method thereof.
Another object of the present invention is to have core-shell composite phase-structured nickel hydroxide not only directly as the positive electrode material of nickel series rechargeable battery, and carry out oxidation and produce and have core-shell composite phase-structured hydroxy nickel oxide and lithium nickelate positive electrode material.
For this reason, technical scheme of the present invention is to adopt the controlled crystallization method to prepare spherical beta phase nickel hydroxide earlier, particularly be doped with the spherical beta phase nickel hydroxide of cobalt and zinc, on spherical beta phase nickel hydroxide nuclear, continue deposition of aluminum then, cobalt, the stable class alpha-phase nickel hydroxide shell that manganese and yttrium replace has core-shell composite phase-structured ball-shape nickel hydroxide thereby make.
Core-shell composite phase-structured nickel hydroxide of the present invention is to be shell with the class alpha-phase nickel hydroxide, and beta phase nickel hydroxide is nuclear, and the mass ratio of class alpha-phase nickel hydroxide and beta phase nickel hydroxide is (0.1～1.0): 1.
Its concrete steps of the preparation method of core-shell composite phase-structured nickel hydroxide of the present invention are as follows:
1) preparation contains the mixing solutions of cobalt salt, zinc salt and nickel salt, be designated as solution A, wherein nickel salt is selected from a kind of in the vitriol, nitrate, chlorate etc. of nickel, cobalt salt is selected from a kind of in vitriol, nitrate, chlorate of cobalt etc., zinc salt is selected from a kind of in vitriol, nitrate, chlorate of zinc etc., the concentration of nickel salt is 1～5M, and the mol ratio of zinc, cobalt and nickel is (3～8): (1～5): 100;
2) compound concentration is sodium hydroxide or the potassium hydroxide solution of 1～8M, is designated as solution B;
3) the preparation quality is 5%～20% ammonia soln than concentration, is designated as solution C;
4) solution A, B and C are added in the reactor, the pH of control reaction solution is 10～13, and the temperature of reaction solution is 30～80 ℃, and the reaction times is 8～72h, gets solidliquid mixture;
5) solidliquid mixture that reaction is obtained carries out solid-liquid separation, and oven dry promptly obtains spherical beta phase nickel hydroxide;
6) preparation contains aluminium salt, cobalt salt, the mixing solutions of at least a and nickel salt in manganese salt and the yttrium salt, be designated as the nickel salt mixing solutions, mix with spherical beta phase nickel hydroxide then, obtain slurries D, wherein the nickel salt in the nickel salt mixing solutions is selected from the vitriol of nickel, nitrate, a kind of in the chlorate etc., aluminium salt is selected from the vitriol of aluminium, nitrate, a kind of in the chlorate etc., cobalt salt is selected from the vitriol of cobalt, nitrate, a kind of in the chlorate etc., manganese salt is selected from the vitriol of manganese, nitrate, a kind of in the chlorate etc., yttrium salt is selected from the vitriol of yttrium, nitrate, a kind of in the chlorate etc., the concentration of nickel salt mixing solutions is 1～5M, aluminium salt, cobalt salt, the summation of the metal ion in manganese salt and the yttrium salt and the mol ratio of nickel ion are (15～25): 100, in the nickel salt mixing solutions in nickel total amount and the spherical beta phase nickel hydroxide mol ratio of nickel total amount be (10～100): 100;
7) sodium hydroxide or the potassium hydroxide solution of preparation 1～10M, and add yellow soda ash or the salt of wormwood that its mass ratio is sodium hydroxide or potassium hydroxide solution 2%～8%, get solution E;
8) solution C, D, E are added in the reactor, the pH of control reaction solution is 10～13, and the temperature of reaction solution is 30～80 ℃, and the reaction times is 8～72h, gets solidliquid mixture;
9) solidliquid mixture that reaction is obtained filters, and promptly obtains after the drying having core-shell composite phase-structured nickel hydroxide.
Core-shell composite phase-structured nickel hydroxide of the present invention is used for the positive electrode material of nickel series rechargeable battery, or is used to have core-shell composite phase-structured hydroxy nickel oxide and lithium nickelate positive electrode material.
Compare with existing technical scheme, the present invention has taken all factors into consideration α and β Ni (OH) mutually
2Advantage separately, providing a kind of is nuclear with spherical beta phase nickel hydroxide, keeps material to have higher tap density; With α-Ni (OH)
2Be shell, make material obtain higher quality than loading capacity, good cycle life and capacity store hold facility.
Embodiment
Embodiment 1
1M nickel sulfate solution and 1M solution of zinc sulfate, 1M cobalt sulfate solution are pressed Ni: Zn: Co=100: 3: 1 mixed is even, then with the oxidation sodium solution of 1M and ammoniacal liquor complexing agent also stream reaction under stirring action of 5%, the pH value of control solution is 10, temperature of reaction is 30 ℃, and the reaction times is 72h.Filter then, with the solid precipitation washes clean, dry the spherical β-Ni (OH) that obtains doping of Zn and Co down at 130 ℃ with deionized water
2
With 1M nickel sulfate solution and 1M alum liquor in Ni: Al=100: 15 ratio uniform mixing, with spherical β-Ni (OH) of doping of Zn and Co
2Add in the nickel salt mixed solution and make slurries, the Ni in the control nickel salt mixed solution and spherical β-Ni (OH) of doping of Zn and Co
2In the ratio of Ni total amount be 10: 100.Then with slurries and the 1M sodium hydroxide solution that contains 8% yellow soda ash, and 10% ammonia soln pumps in the reactor, and the pH of control reaction solution is 11, and the temperature of reaction solution is 30 ℃, reaction 8h.Filter then, with deionized water with the solid precipitation washes clean, at 60 ℃ of spherical β-Ni (OH) that are drying to obtain with doping of Zn and Co
2Be nuclear, Al replaces α-Ni (OH)
2Composite phase-structured spherical Ni (OH) for shell
2, this sample note is made N1.
Embodiment 2
Nickel chloride solution and 2M liquor zinci chloridi, the 2M cobalt chloride solution of 2M are pressed Ni: Zn: Co=100: 5: 2 mixed is even, then with the potassium hydroxide solution of 2M and ammoniacal liquor complexing agent also stream reaction under stirring action of 10%, the pH value of control solution is 10.5, temperature of reaction is 50 ℃, and the reaction times is 48h.Filter then, with gained solid precipitation washes clean, dry the spherical β-Ni (OH) that obtains doping of Zn and Co down at 120 ℃ with deionized water
2
With 2M nickel chloride solution and 2M aluminum chloride and 2M cobalt chloride solution in Ni: Al: Co=100: 20: 5 ratio uniform mixing, with spherical β-Ni (OH) of doping of Zn and Co
2Add in the nickel salt mixed solution and make slurries, the Ni in the control nickel salt mixed solution and spherical β-Ni (OH) of doping of Zn and Co
2In the ratio of Ni total amount be 20: 100.Then with slurries and the 5M potassium hydroxide solution that contains 5% salt of wormwood, and 20% ammonia soln pumps in the reactor, and the pH of control reaction solution is 11, and the temperature of reaction solution is 50 ℃, reaction 24h.Filter then, with deionized water with the solid precipitation washes clean, at 50 ℃ of spherical β-Ni (OH) that are drying to obtain with doping of Zn and Co
2Be nuclear, Al and Co replace α-Ni (OH)
2Composite phase-structured spherical Ni (OH) for shell
2, this sample note is made N2.
Embodiment 3
Nickel nitrate solution and 3M zinc nitrate solution, the 3M cobalt nitrate solution of 3M are pressed Ni: Zn: Co=100: 7: 4 mixed is even, then with the sodium hydroxide solution of 5M and ammoniacal liquor complexing agent also stream reaction under stirring action of 20%, the pH value of control solution is 11, temperature of reaction is 60 ℃, and the reaction times is 36h.Filter then, with the solid precipitation washes clean, dry the spherical β-Ni (OH) that obtains doping of Zn and Co down at 100 ℃ with deionized water
2
With the cobalt chloride solution of the aluminum chloride of the nickel chloride solution of 3M and 3M and 3M in Ni: Al: Co=100: 20: 5 ratio uniform mixing, with spherical β-Ni (OH) of doping of Zn and Co
2Add in the nickel salt mixed solution and make slurries, the Ni in the control nickel salt mixed solution and spherical β-Ni (OH) of doping of Zn and Co
2In the ratio of Ni total amount be 50: 100.Then with slurries and the 5M potassium hydroxide solution that contains 3% salt of wormwood, and 10% ammonia soln pumps in the reactor, and the pH of control reaction solution is 11, and the temperature of reaction solution is 50 ℃, reaction 24h.Filter then, with deionized water with the solid precipitation washes clean, at 100 ℃ of spherical β-Ni (OH) that are drying to obtain with doping of Zn and Co
2Be nuclear, Al and Co replace α-Ni (OH)
2Composite phase-structured spherical Ni (OH) for shell
2, this sample note is made N3.
Embodiment 4
Nickel sulfate solution and 4M solution of zinc sulfate, the 4M cobalt sulfate solution of 4M are pressed Ni: Zn: Co=100: 6: 3 mixed is even, then with the sodium hydroxide solution of 6M and ammoniacal liquor complexing agent also stream reaction under stirring action of 10%, the pH value of control solution is 12, temperature of reaction is 60 ℃, and the reaction times is 18h.Filter then, with the solid precipitation washes clean, dry the spherical β-Ni (OH) that obtains doping of Zn and Co down at 100 ℃ with deionized water
2
With the manganese chloride solution of the aluminum chloride of the nickel chloride solution of 4M and 4M and 4M in Ni: Al: Mn=100: 10: 10 ratio uniform mixing, with spherical β-Ni (OH) of doping of Zn and Co
2Add in the nickel salt mixed solution and make slurries, the Ni in the control nickel salt mixed solution and spherical β-Ni (OH) of doping of Zn and Co
2In the ratio of Ni total amount be 80: 100.Then with slurries and the 5M potassium hydroxide solution that contains 2% salt of wormwood, and 10% ammonia soln pumps in the reactor, and the pH of control reaction solution is 11, and the temperature of reaction solution is 50 ℃, reaction 24h.Filter then, with deionized water with the solid precipitation washes clean, at 130 ℃ of spherical β-Ni (OH) that are drying to obtain with doping of Zn and Co
2Be nuclear, Al and Co replace α-Ni (OH)
2Composite phase-structured spherical Ni (OH) for shell
2, this sample note is made N4.
Embodiment 5
Nickel sulfate solution and 5M solution of zinc sulfate, the 5M cobalt sulfate solution of 5M are pressed Ni: Zn: Co=100: 8: 5 mixed is even, then with the sodium hydroxide solution of 8M and ammoniacal liquor complexing agent also stream reaction under stirring action of 5%, the pH value of control solution is 13, temperature of reaction is 80 ℃, and the reaction times is 8h.Filter then, with the solid precipitation washes clean, dry the spherical β-Ni (OH) that obtains doping of Zn and Co down at 30 ℃ with deionized water
2
With the yttrium nitrate solution of the aluminum nitrate of the nickel nitrate solution of 5M and 5M and 5M in Ni: Al: Y=100: 20: 5 ratio uniform mixing, with spherical β-Ni (OH) of doping of Zn and Co
2Add in the nickel salt mixed solution and make slurries, the Ni in the control nickel salt mixed solution and spherical β-Ni (OH) of doping of Zn and Co
2In the ratio of Ni total amount be 100: 100.Then with slurries and the 5M potassium hydroxide solution that contains 2% salt of wormwood, and 10% ammonia soln pumps in the reactor, and the pH of control reaction solution is 11, and the temperature of reaction solution is 50 ℃, reaction 24h.Filter then, with deionized water with the solid precipitation washes clean, at 130 ℃ of spherical β-Ni (OH) that are drying to obtain with doping of Zn and Co
2Be nuclear, Al and Co replace α-Ni (OH)
2Composite phase-structured spherical Ni (OH) for shell
2, this sample note is made N5.
Comparative Examples 1
Nickel nitrate solution and 3M zinc nitrate solution, the 3M cobalt nitrate solution of 3M are pressed Ni: Zn: Co=100: 5: 3 mixed is even, then with the sodium hydroxide solution of 5M and ammoniacal liquor complexing agent also stream reaction under stirring action of 15%, the pH value of control solution is 11, temperature of reaction is 60 ℃, and the reaction times is 36h.Filter then, with the solid precipitation washes clean, dry the spherical β-Ni (OH) that obtains doping of Zn and Co down at 100 ℃ with deionized water
2, this comparative example note is made D1
Comparative Examples 2
With 1M nickel sulfate solution and 1M alum liquor in Ni: Al=100: 20 ratio uniform mixing, with the 1M sodium hydroxide solution that contains 8% yellow soda ash, and 15% ammonia soln pumps in the reactor, and the pH of control reaction solution is 12, the temperature of reaction solution is 30 ℃, reaction 48h.Filter then, with the solid precipitation washes clean, be drying to obtain Al at 60 ℃ and replace α-Ni (OH) with deionized water
2, this comparative example note is made D2.
In order to examine or check nickel hydroxide charging oxidation state is the stability in storage of hydroxy nickel oxide (NiOOH) in alkaline electrolyte, its corresponding hydroxy nickel oxide immersed survey the amount of oxidation that its self-discharge branch parses in 60 ℃ the 6M potassium hydroxide electrolyte and compare, the amount of oxidation of separating out bright its storge quality of saving your breath more is good more.This is because the hydroxy nickel oxide that nickel hydroxide generates after the charging oxidation at alkaline electrolyte year self-discharge decomposition reaction as follows can take place:
2NiOOH+H
2O→2Ni(OH)
2+1/2O
2
Nickel hydroxide phase inductive charging oxidation state NiOOH with nickel hydroxide in the potassium hydroxide solution of 6M in 60 ℃ down with the Potassium Persulphate oxidation 8h of 4 times of quality, filter then, clean with deionized water wash, dry and get for 60 ℃.This also is one of method for preparing with the compound beta-phase nickel hydroxide of nucleocapsid the compound phase hydroxy nickel oxide of nucleocapsid.
The performance of each sample is as shown in table 1.The compound phase ball-shape nickel hydroxide of nucleocapsid has than Al replacement α-Ni (OH) as can be seen from Table 1
2High tap density can be filled into higher active substance like this in limited battery space, make cell container higher.The compound phase ball-shape nickel hydroxide of nucleocapsid also has than β-Ni (OH)
2High specific discharge capacity makes that the utilization ratio of nickel is more abundant, and cell container is higher.Particularly the compound phase ball-shape nickel hydroxide of nucleocapsid is at the existing widely used spherical β-Ni (OH) of Charging state ratio
2Much better storge quality is arranged, can make the battery of Charging state that arranged longer storage time like this, especially the favorable actual application meaning is arranged for high capacity cell.
Table 1
| The sample title | The ratio of shell nuclear phase nickel | Tap density (g/cm 3) | 0.1C specific discharge capacity (mAh/g) | Gassing rate (cm 3/g·m) |
| N1 | 0.1 | 2.06 | 270 | 0.31 |
| N2 | 0.2 | 2.01 | 287 | 0.27 |
| N3 | 0.5 | 1.83 | 309 | 0.23 |
| N4 | 0.8 | 1.75 | 318 | 0.22 |
| N5 | 1.0 | 1.71 | 330 | 0.21 |
| D1 | \ | 2.15 | 263 | 6.83 |
| D2 | \ | 1.57 | 387 | 0.18 |
Claims (8)
1. core-shell composite phase-structured nickel hydroxide is characterized in that the class alpha-phase nickel hydroxide that replaces with aluminium, cobalt, manganese and/or yttrium is a shell, is nuclear with the beta phase nickel hydroxide of doping cobalt and zinc, and the mass ratio of class alpha-phase nickel hydroxide and beta phase nickel hydroxide is 0.1～1.0: 1.
2. the preparation method of core-shell composite phase-structured nickel hydroxide as claimed in claim 1 is characterized in that its concrete steps are as follows:
1) preparation contains the mixing solutions of cobalt salt, zinc salt and nickel salt, is designated as solution A;
2) compound concentration is sodium hydroxide or the potassium hydroxide solution of 1～8M, is designated as solution B;
3) the preparation quality is 5%～20% ammonia soln than concentration, is designated as solution C;
4) solution A, B and C are added in the reactor, get solidliquid mixture;
5) solidliquid mixture that reaction is obtained carries out solid-liquid separation, and oven dry promptly obtains spherical beta phase nickel hydroxide;
6) preparation contains the mixing solutions of at least a and nickel salt in aluminium salt, cobalt salt, manganese salt and the yttrium salt, is designated as the nickel salt mixing solutions, mixes with spherical beta phase nickel hydroxide then, obtains slurries D;
7) sodium hydroxide or the potassium hydroxide solution of preparation 1～10M, and add yellow soda ash or the salt of wormwood that its mass ratio is sodium hydroxide or potassium hydroxide solution 2%～8%, get solution E;
8) solution C, D, E are added in the reactor, get solidliquid mixture;
9) solidliquid mixture that reaction is obtained filters, and promptly obtains after the drying having core-shell composite phase-structured nickel hydroxide.
3. the preparation method of core-shell composite phase-structured nickel hydroxide as claimed in claim 2, it is characterized in that in step 1), nickel salt is selected from a kind of in the vitriol, nitrate, chlorate of nickel, cobalt salt is selected from a kind of in the vitriol, nitrate, chlorate of cobalt, zinc salt is selected from a kind of in the vitriol, nitrate, chlorate of zinc, the concentration of nickel salt is 1～5M, and the mol ratio of zinc, cobalt and nickel is 3～8: 1～5: 100.
4. the preparation method of core-shell composite phase-structured nickel hydroxide as claimed in claim 2 is characterized in that in step 4), and the pH of control reaction solution is 10～13, and the temperature of reaction solution is 30～80 ℃, and the reaction times is 8～72h.
5. the preparation method of core-shell composite phase-structured nickel hydroxide as claimed in claim 2, it is characterized in that in step 6), nickel salt in the nickel salt mixing solutions is selected from the vitriol of nickel, nitrate, a kind of in the chlorate, aluminium salt is selected from the vitriol of aluminium, nitrate, a kind of in the chlorate, cobalt salt is selected from the vitriol of cobalt, nitrate, a kind of in the chlorate, manganese salt is selected from the vitriol of manganese, nitrate, a kind of in the chlorate, yttrium salt is selected from the vitriol of yttrium, nitrate, a kind of in the chlorate, the concentration of nickel salt mixing solutions is 1～5M, aluminium salt, cobalt salt, the summation of the metal ion in manganese salt and the yttrium salt and the mol ratio of nickel ion are 15～25: 100, in the nickel salt mixing solutions in nickel total amount and the spherical beta phase nickel hydroxide mol ratio of nickel total amount be 10～100: 100.
6. the preparation method of core-shell composite phase-structured nickel hydroxide as claimed in claim 2 is characterized in that in step 8), and the pH of control reaction solution is 10～13, and the temperature of reaction solution is 30～80 ℃, and the reaction times is 8～72h.
7. core-shell composite phase-structured nickel hydroxide as claimed in claim 1 is applied to the positive electrode material of nickel series rechargeable battery.
8. core-shell composite phase-structured nickel hydroxide as claimed in claim 1 is applied to have core-shell composite phase-structured hydroxy nickel oxide and lithium nickelate positive electrode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1313245A (en) * | 2001-03-20 | 2001-09-19 | 北京科海迈迪生物技术有限责任公司 | Process for preparing nm-class beta-plase composite nickel hydroxide |
| JP2005194156A (en) * | 2004-01-09 | 2005-07-21 | Ishikawajima Harima Heavy Ind Co Ltd | Method of manufacturing nickel hydroxide powder |
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| CN1313245A (en) * | 2001-03-20 | 2001-09-19 | 北京科海迈迪生物技术有限责任公司 | Process for preparing nm-class beta-plase composite nickel hydroxide |
| JP2005194156A (en) * | 2004-01-09 | 2005-07-21 | Ishikawajima Harima Heavy Ind Co Ltd | Method of manufacturing nickel hydroxide powder |
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