CN1884101A - 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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- CN1884101A CN1884101A CNA2006100919083A CN200610091908A CN1884101A CN 1884101 A CN1884101 A CN 1884101A CN A2006100919083 A CNA2006100919083 A CN A2006100919083A CN 200610091908 A CN200610091908 A CN 200610091908A CN 1884101 A CN1884101 A CN 1884101A
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- nickel
- salt
- nickel hydroxide
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- 150000002815 nickel Chemical class 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 150000003746 yttrium Chemical class 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 3
- 150000001805 chlorine compounds Chemical class 0.000 claims 2
- 150000002823 nitrates Chemical class 0.000 claims 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- 239000011702 manganese sulphate Substances 0.000 claims 1
- 235000007079 manganese sulphate Nutrition 0.000 claims 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 claims 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 32
- 229910052725 zinc Inorganic materials 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000011572 manganese Chemical group 0.000 abstract description 3
- 229910052727 yttrium Chemical group 0.000 abstract description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910018661 Ni(OH) Inorganic materials 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- BAPRMBRFVUJBEI-UHFFFAOYSA-N [O].[O].[Ni] Chemical compound [O].[O].[Ni] BAPRMBRFVUJBEI-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
核壳复合相结构氢氧化镍及其制备方法与应用，涉及一种电池正极材料，尤其是涉及一种具有核壳复合相结构的氢氧化镍电池正极材料及其制备方法与应用。提供一种以球形β相氢氧化镍为核，保持材料具有较高的振实密度；以α－Ni(OH) 2为壳，使材料获得较高的质量比放电容量，良好的循环寿命及容量储存保持能力，具有核壳复合相结构的氢氧化镍正极材料及其制备方法。以α相氢氧化镍为壳，β相氢氧化镍为核，α相氢氧化镍与β相氢氧化镍的质量比为0.1～1.0∶1。用受控结晶法制备球形β相氢氧化镍，特别是掺杂有钴与锌的球形β相氢氧化镍，在球形β相氢氧化镍核上继续沉积铝，钴，锰及钇取代的稳定的α相氢氧化镍壳，得产物。The core-shell composite phase structure nickel hydroxide and its preparation method and application relate to a battery positive electrode material, in particular to a nickel hydroxide battery positive electrode material with a core-shell composite phase structure and its preparation method and application. Provide a spherical β-phase nickel hydroxide as the core to keep the material with a high tap density; use α-Ni(OH) 2 as the shell to enable the material to obtain a higher mass specific discharge capacity, good cycle life and Capacity storage retention capacity, nickel hydroxide positive electrode material with core-shell composite phase structure and preparation method thereof. The α-phase nickel hydroxide is used as the shell, the β-phase nickel hydroxide is used as the core, and the mass ratio of the α-phase nickel hydroxide to the β-phase nickel hydroxide is 0.1-1.0:1. Prepare spherical β-phase nickel hydroxide by controlled crystallization method, especially spherical β-phase nickel hydroxide doped with cobalt and zinc, and continue to deposit aluminum, cobalt, manganese and yttrium substitution on the spherical β-phase nickel hydroxide nucleus. The α-phase nickel hydroxide shell, the product.
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:
Oxygen nickel oxide 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 |
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| CN112366309A (en) * | 2020-11-23 | 2021-02-12 | 中伟新材料股份有限公司 | Magnesium-doped nickel-cobalt binary precursor and preparation method thereof, lithium ion battery positive electrode material and lithium ion battery |
| WO2024114720A1 (en) * | 2022-11-30 | 2024-06-06 | 华为技术有限公司 | Positive electrode material, preparation method therefor and use thereof |
| CN119284988A (en) * | 2024-10-30 | 2025-01-10 | 金驰能源材料有限公司 | Cobalt-free NiMnAl precursor with composite structure and preparation method thereof, positive electrode material, lithium ion battery and electrical equipment |
| WO2025097298A1 (en) * | 2023-11-07 | 2025-05-15 | 广东邦普循环科技有限公司 | Positive electrode material and precursor thereof, preparation method therefor and battery |
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| CN1164500C (en) * | 2001-03-20 | 2004-09-01 | 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 for producing nickel hydroxide powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112366309A (en) * | 2020-11-23 | 2021-02-12 | 中伟新材料股份有限公司 | Magnesium-doped nickel-cobalt binary precursor and preparation method thereof, lithium ion battery positive electrode material and lithium ion battery |
| WO2024114720A1 (en) * | 2022-11-30 | 2024-06-06 | 华为技术有限公司 | Positive electrode material, preparation method therefor and use thereof |
| WO2025097298A1 (en) * | 2023-11-07 | 2025-05-15 | 广东邦普循环科技有限公司 | Positive electrode material and precursor thereof, preparation method therefor and battery |
| CN119284988A (en) * | 2024-10-30 | 2025-01-10 | 金驰能源材料有限公司 | Cobalt-free NiMnAl precursor with composite structure and preparation method thereof, positive electrode material, lithium ion battery and electrical equipment |
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