CN1893151A - Method for preparing lithium composite metal oxide - Google Patents
Method for preparing lithium composite metal oxide Download PDFInfo
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- CN1893151A CN1893151A CNA2005100357397A CN200510035739A CN1893151A CN 1893151 A CN1893151 A CN 1893151A CN A2005100357397 A CNA2005100357397 A CN A2005100357397A CN 200510035739 A CN200510035739 A CN 200510035739A CN 1893151 A CN1893151 A CN 1893151A
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- China
- Prior art keywords
- preparation
- metal oxide
- lithium
- solution
- lini
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 13
- 239000002131 composite material Substances 0.000 title abstract 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 55
- 238000002360 preparation method Methods 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910013716 LiNi Inorganic materials 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000003483 aging Methods 0.000 claims description 12
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 11
- -1 cobalt complex hydroxide Chemical class 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910012741 LiNi0.5Co0.5O2 Inorganic materials 0.000 claims description 3
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 3
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 14
- 230000000536 complexating effect Effects 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000010981 drying operation Methods 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 23
- 239000007774 positive electrode material Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 238000010792 warming Methods 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000006183 anode active material Substances 0.000 description 11
- 229910017709 Ni Co Inorganic materials 0.000 description 10
- 229910003267 Ni-Co Inorganic materials 0.000 description 10
- 229910003262 Ni‐Co Inorganic materials 0.000 description 10
- 206010013786 Dry skin Diseases 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 230000002950 deficient Effects 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- CDPUAMYMANXCAH-UHFFFAOYSA-N azane cobalt nickel Chemical compound N.[Co].[Ni] CDPUAMYMANXCAH-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 235000006748 manganese carbonate Nutrition 0.000 description 4
- 239000011656 manganese carbonate Substances 0.000 description 4
- 229940093474 manganese carbonate Drugs 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 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 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- QDWNJWYHGDYFOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[Li] Chemical compound [N+](=O)(O)[O-].[Li] QDWNJWYHGDYFOG-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 1
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Images
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The method for preparing composite metal oxide of lithium includes following steps: preparing mixed complexing solution of nickel and/or cobalt and ammonia; adding mixed ammonia complexing solution and alkali solution to reaction kettle slowly so as to generate composite hydroxide of nickel and/or cobalt through coprecipitation method; obtaining precursor body after aging, separating, washing, and drying operations; mix grinding the obtained precursor body and lithium hydroxide or lithium salt and metal M salt or its oxide; heat treating the admixture under 150-550 deg.C and heat treating the obtained object under 650-850 deg.C so as to obtain composite metal oxide of lithium. Features are: even granularity in spheroidicity, larger density, steady structure, good machining action, excellent performance of electrochemical charge and discharge and circulation.
Description
Technical field
The present invention relates to preparation method as the lithium complex metal oxide of positive electrode material of lithium secondary cell.
Background technology
The preparation of novel anode material is one of key technology of restriction lithium secondary battery fast development.The positive electrode that is commonly used for lithium ion battery at present has cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2), spinel lithium manganate (LiMn
2O
4), layer structure LiMn2O4 (LiMnO
2) and their doped compound.Cobalt acid lithium is a commercialization anode material for lithium-ion batteries commonly used at present, and preparation technology is very ripe, but because of its natural resources shortage, costs an arm and a leg, and is used as electrokinetic cell poor stability etc. simultaneously, thereby has limited the extensive use of cobalt acid lithium.Lithium nickelate has and the identical layer structure of cobalt acid lithium, and similar performance, (specific discharge capacity is with exceeding 40～50mAh/g) than cobalt acid lithium under the condition to have height ratio capacity as lithium ion secondary battery anode material, aboundresources, advantages such as low price, but have in the lithium nickelate difficulty, poor heat stability, cyclic process of synthetic chemistry metering ratio shortcomings such as the capacity retentivity is bad.
LiNi
xCo
1-xO
2And the mixed oxide of multi-element metal doping vario-property has not only possessed LiCoO
2Characteristic (easily synthetic, stable performance), more have LiNiO concurrently
2Height ratio capacity, advantage cheaply.And in charge and discharge process LiNi
xCo
1-xO
2And pure LiNiO does not take place in the mixed oxide of multi-element metal doping vario-property
2Three phase transformations that material experienced, thereby have better cycle performance, simultaneously, its irreversible capacity can provide the lithium source for the formation of negative pole SEI film, thereby reduces anodal overhead provision.
At present, LiNi
xCo
1-xO
2And the mixed oxide of multi-element metal doping vario-property synthetic method commonly used has ion-exchange, wet chemistry method and solid reaction process etc.Ion-exchange step complexity, the expense costliness; Wet chemistry method separation and washing be difficulty, complex operation, production poor repeatability, product lack of homogeneity; And the solid phase reaction rule is difficult to make each component to mix.
Application number is that 98121447.9 Chinese patent has proposed a kind of ammoniacal liquor to be added reactor with alkali lye, make metal ion and ammonia and alkali lye between form competitive reaction, thereby reach the purpose of controls reaction speed.Experimental result shows: adopt the particle diameter of this method control intermediate difficult, the also difficult control of the intermediate pattern of formation.The size of product pellet and pattern are difficult to control.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of preparation technology size and pattern simple, that produce good reproducibility, product good uniformity, particle to be easy to control, and have the preparation method of the lithium complex metal oxide of excellent charging and discharging performance and cyclical stability.
For solving the problems of the technologies described above, technical scheme of the present invention is: general formula is that the preparation method of the lithium complex metal oxide of formula (I) mainly may further comprise the steps:
Li
a(Ni
bCo
c)M
1-b-cO
2 (I)
A=0.97-1.07 wherein, 0≤b≤1,0≤c≤1,0.5≤b+c≤1
(a) complex solution that mixes of preparation nickel and/or cobalt and ammonia;
(b) will mix ammino and close in solution and the slow simultaneously adding reactor of aqueous slkali, co-precipitation generates nickel and/or cobalt complex hydroxide, makes presoma after ageing, separation, washing, drying;
(c) presoma that (b) step is made and lithium hydroxide or lithium salts and metal M salt or its element source oxide carry out mix grinding;
(d) in 150-550 ℃ of this mixture of following heat treatment, and;
(e) product of gained makes described lithium complex metal oxide in 650-850 ℃ of following heat treatment step (d).
Described step (a) is to be prepared in ammoniacal liquor cushioning liquid and formed and mix complex solution by nickel and/or cobalt salt.
Mixing the preparation environment that ammino closes solution in the described step (a) is the cushioning liquid that the pH value equals 8-11, and cushioning liquid is made up of ammoniacal liquor and amine salt or ammoniacal liquor and weak acid.
The saline solution concentration of described step (a) is 0.5-4mol/L, and the 0.5-3 that the middle concentration of lye of step (b) is described saline solution concentration doubly.
The temperature of coprecipitation reaction is 40-80 ℃ in the described step (b), and the mixing speed of blender is 200-1000 rev/min during reaction, and the time of coprecipitation reaction is 4-10 hour; Described digestion time was at least 1 hour; Described alkali lye is at least a among NaOH, KOH or the LiOH, and the pH value of solution is 10～12 during reaction.
Drying is to be 60-120 ℃ of dry nickel and/or a cobalt complex hydroxide material 8-36 hour down at baking temperature in the described step (b).
Metal M salt in the described step (c) comprises at least a in nitrate, carbonate, organic salt or its element source oxide of metal M.
The metal M of the metal M salt in the described step (c) is at least a in aluminium, iron, manganese, titanium, copper, calcium, zinc and the chromium.
Described step (d) heat treatment time is 2-8 hour; Described step (e) heat treatment time is 6-26 hour.
Described lithium complex metal oxide is LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2, LiNiO
2, LiCoO
2, LiNi
0.5Co
0.5O
2, LiNi
0.4Co
0.1Mn
0.4Al
0.05Fe
0.05O
2, LiNi
1/3Co
1/3Mn
1/3O
2, LiNi
0.7Co
0.15Mn
0.1Ti
0.03Cu
0.02O
2, Li (Ni
1/3Co
1/3Mn
1/3)
0.95Zn
0.02Ca
0.01Ti
0.02O
2, or LiNi
0.8Co
0.1Mn
0.05Al
0.02Cr
0.02Ti
0.01O
2, wherein prepare LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Be in step (b), will mix ammino to close solution and aqueous slkali and aluminum salt solution and slowly add in the reactor simultaneously and carry out coprecipitation reaction.
The invention has the beneficial effects as follows: (1) preparation method of the present invention prepares the complex solution that mixes of nickel and/or cobalt and ammonia earlier, again with the alkali lye coprecipitation reaction, metal ion in the complex solution is released lentamente along with the carrying out of precipitation reaction, there is a process of growing up in particle, temperature during by the control reaction, pH value and mixing speed just can more easily be controlled the size and the pattern of particle, and can generate the ellipsoidal particle of uniform particle diameter, be easy to separate, washing precipitation, with can obtain the particle of similar pattern behind other doped chemical mixed sintering, thereby help improving the cycle performance and the pole piece processing behavior of material, also be convenient to the processing again of material.(2) the lithium complex metal oxide positive electrode active materials that adopts method of the present invention to prepare, its XRD test result shows: this active material is a layer structure, and crystalline form is grown very good, structural integrity, the ratio at I003 and I104 peak is more than 1.2, and do not have other impurity peaks and occur; Electrochemical property test shows: the processing behavior of the cycle performance of material, capacity retentivity and pole piece has all reached requirement on industrial application; SEM test result display material particle size distribution is even, and particle constitutes elliposoidal structure second particle by the primary particle of class square structure, and the average grain diameter of second particle is at 4-25 μ m, and tap density is 2.15-2.50g/cm3.(3) method of the present invention adopts coprecipitation reaction to combine with solid phase reaction, help controlling the pattern and the particle size of particle on the one hand, realized also that on the other hand material key component element makes up by atomic level, simultaneously, solid phase reaction can be modified the surface and the structure of material, thereby make the stability of material good, this preparation method not only process is simple, and it is workable to have technology, produce good reproducibility, characteristics such as product good uniformity are easy to realize industrialization, and cost is relatively low.
The invention will be further described below in conjunction with drawings and Examples, will help further to understand method of the present invention and advantage, but embodiment is only for understanding the present invention.
Description of drawings
Fig. 1 is the X diffraction pattern (XRD) of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
Fig. 2 is the sem photograph (SEM) of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
Fig. 3 is the first charge-discharge curve chart of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
Fig. 4 is the charge-discharge performance figure of the anode active material of lithium ion secondary battery of embodiment 1 preparation.
Fig. 5 is the sem photograph (SEM) of the anode active material of lithium ion secondary battery of embodiment 2 preparations.
Fig. 6 is the X diffraction pattern (XRD) of the anode active material of lithium ion secondary battery of embodiment 2 preparations.
Fig. 7 is the first charge-discharge curve chart of the anode active material of lithium ion secondary battery of embodiment 2 preparations.
Fig. 8 is the sem photograph (SEM) of the anode active material of lithium ion secondary battery of embodiment 5 preparations.
Fig. 9 is the X diffraction pattern (XRD) of the anode active material of lithium ion secondary battery of embodiment 5 preparations.
Figure 10 is the first charge-discharge curve chart of the anode active material of lithium ion secondary battery of embodiment 5 preparations.
Figure 11 is the first charge-discharge curve chart of the anode active material of lithium ion secondary battery of embodiment 6 preparations.
Embodiment
The preparation method who contains the multi-component oxide of cobalt nickel, be earlier in the pH value is 8～11 ammoniacal liquor-amine salt or ammoniacal liquor-weak acid cushioning liquid, the complex solution that mixes of preparation nickel cobalt and ammonia, then slowly add in the reactor simultaneously and carry out coprecipitation reaction with alkali lye, wherein, the coprecipitation reaction time is 4-10 hour, reaction temperature is 40-80 ℃, mixing speed is 240-1000rpm, generate the Ni-Co complex hydroxide, ageing separates, washing Ni-Co complex hydroxide, it is even to make particle diameter, density is bigger, an elliposoidal Ni-Co complex hydroxide material of chemical property excellence; Baking temperature be under 60-120 ℃ air atmosphere or the vacuum environment a dry Ni-Co complex hydroxide material after 8-36 hour with nitrate, carbonate, organic salt or its element source oxide of lithium hydroxide or lithium salts and M at least a mix grinding even, and in 150-550 ℃ of this mixture of following heat treatment 2-8 hour; And then, promptly get the lithium complex metal oxide that contains cobalt nickel in 650-850 ℃ of this mixture of following heat treatment 6-26 hour.
Example 1
This example is to positive electrode active materials LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Preparation and performance structure test specifically describe.
Got nickel (Ni) in 0.75: 0.1 in molar ratio respectively, 8.5 moles in the sulfate of cobalt (Co) adds water and is made into 1.7M (M is the abbreviation of mol/L, solution down together), under continuous stirring condition, slowly add the pH value of preparing by ammoniacal liquor and sulfuric acid amine and be in 10 the cushioning liquid, make nickel cobalt ammino and close solution 10L, under continuous stirring state, with itself and 10L, 2.2MNaOH and 0.1MAl
2(SO
4)
3Mixed aqueous solution slowly splash into simultaneously and fill the 7L aqueous solution and regulate in the reactor of its pH value to 11 with the pure NaOH solution of 2.2M, reaction temperature is 40 ℃, mixing speed is 400rpm.Isolate the Ni-Co-Al complex hydroxide after 6 hours, ageing after 2 hours with behind the distilled water washing several times in 80 ℃ of dryings 16 hours, make presoma after grinding, sieving, accurately measure behind its moisture content and manganese carbonate and monohydrate lithium hydroxide (LiOHH
2O) 1: 0.053: 1.06 in molar ratio mix grinding is placed in the Based Intelligent Control Muffle furnace, in dry air, be warming up to 320 ℃ and constant temperature and carried out the heat treatment first time in 6 hours with 2 ℃/min, then be warming up to 750 ℃ and constant temperature and carried out clinkering in 16 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: XRD figure is composed as shown in Figure 1, with LiCoO
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.9, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates of Fig. 2 shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and recording its average grain diameter is 5-16 μ m, and the tap density of powder is 2.19g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige.The negative pole of button cell is a lithium metal, barrier film is a glass fiber filter paper, positive pole is made by this synthetic product, the method for making of its positive plate is similar to macrocell pole piece method for making, be about to 92 parts of products of the present invention, 4 parts of conductive agents, 4 parts of binding agent PVDF (Kynoar) and an amount of solvent NMP (N-methyl pyrrolidone) mixing stirring and make slurry, it is thick then it to be coated with the about 160um of single face on aluminium foil, oven dry, compacting into about 110um after, get the disk of the about 18mm of diameter with puncher, its vacuumize was assembled into 2430 model button cells in 8～12 hours in glove box.Lie prostrate with 0.1C constant current charge to 4.3, behind the 4.3V constant voltage charge, lie prostrate with 0.1C constant-current discharge to 2.75, the initial charge specific capacity that records positive electrode of the present invention is 196.2258mAh/g, and first discharge specific capacity is 167.2495mAh/g, and coulombic efficiency was 85.23% (as shown in Figure 3); The reversible specific capacity that circulates after 100 times is 160.2937mAh/g, and capability retention is 97.00%, electrochemistry cycle performance very excellent (as shown in Figure 4).The slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Example 2
This example is to positive electrode active materials LiNi
0.5Co
0.5O
2Preparation and performance structure test specifically describe.
Got 10 moles in the sulfate of nickel (Ni), cobalt (Co) in 0.5: 0.5 in molar ratio respectively, after thin up becomes 4L solution, constantly slowly adding under the stirring condition by ammoniacal liquor and boric acid (H
3BO
3) the pH value of preparation is in 9 the cushioning liquid, make nickel cobalt ammonia mixing complex solution 10L, under continuous stirring state, with itself and 10L, 2.2MNaOH mixed aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 11.5 with the pure NaOH solution of 2.2M, reaction temperature is 50 ℃, and mixing speed is 500rpm.7.5 isolate the Ni-Co complex hydroxide after hour, ageing filter after 2 hours and with behind the distilled water washing several times in 90 ℃ of dryings 10 hours, make presoma after grinding, sieving, be placed in the Based Intelligent Control Muffle furnace with 1: 0.53 in molar ratio mix grinding of lithium carbonate after accurately measuring its moisture content, in dry air, be warming up to 450 ℃ and constant temperature and carried out the heat treatment first time in 4 hours with 5 ℃/min, then be warming up to 780 ℃ and the constant temperature 12 little anti-clinkerings of carrying out with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
XRD figure spectrum and the LiCoO of the structure of present embodiment products therefrom, pattern test result: Fig. 6
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.6, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates of Fig. 5 shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 5-12 μ m, and the tap density of powder is 2.31g/cm
3Please refer to Fig. 7, the chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 200.6183mAh/g, and first discharge specific capacity is 181.5037mAh/g, and coulombic efficiency is 90.47%; Circulating, capability retention is 94.29% after 100 times, and reversible capacity reaches 171.1400mAh/g.The slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Example 3
This example is to positive electrode active materials LiCoO
2(b=0, preparation method c=1) specifically describes.
Take by weighing 2 moles of cobaltous sulfates, after adding water and being made into 0.2L solution, under continuous stirring condition, slowly add the pH value of preparing by ammoniacal liquor and ammonium nitrate and be in 8 the cushioning liquid, make the cobalt ammino and close solution 0.5L, under continuous stirring state, with itself and 0.5L, the 5M KOH aqueous solution slowly splashes into and fill the 0.2L aqueous solution and regulate in the reactor of its pH value to 11 with the pure KOH solution of 5M simultaneously, reaction temperature is 80 ℃, and mixing speed is 1000rpm.Isolate hydroxide after 7 hours, ageing after 2 hours with behind the distilled water washing several times in 60 ℃ of dryings 24 hours, make presoma after grinding, sieving, accurately measure behind its moisture content and anhydrous nitric acid lithium (LiNO
3) mix grinding was placed in the Based Intelligent Control Muffle furnace in 1: 1.05 in molar ratio, in dry air, be warming up to 500 ℃ and constant temperature and carried out the heat treatment first time in 4 hours with 2 ℃/min, then be warming up to 750 ℃ and constant temperature and carried out clinkering in 20 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.The ESEM (SEM) of institute's prepared material shows that its pattern is an elliposoidal, and structure XRD test result shows that its layer structural development is good, and (not shown) appears in the free from admixture peak.
Example 4
This example is to positive electrode active materials LiNiO
2(b=1, preparation method c=0) specifically describes.
Take by weighing 1 mole of nickelous sulfate, after being made into the aqueous solution of 3.5M, under continuous stirring condition, slowly add the pH value of preparing by ammoniacal liquor and sulfuric acid amine and be in 11 the cushioning liquid, make the nickel ammino and close solution 0.5L, under continuous stirring state, with itself and 0.5L, the 2.2M NaOH aqueous solution slowly splashes into and fill the 0.2L aqueous solution and regulate in the reactor of its pH value to 12 with the pure NaOH solution of 2.2M simultaneously, reaction temperature is 70 ℃, and mixing speed is 800rpm.Isolate hydroxide after 8 hours, ageing after 2 hours with behind the distilled water washing several times in 60 ℃ of dryings 24 hours, make presoma after grinding, sieving, accurately measure behind its moisture content and monohydrate lithium hydroxide (LiOHH
2O) 1: 1.06 in molar ratio mix grinding is placed in the Based Intelligent Control Muffle furnace, in dry air, be warming up to 400 ℃ and constant temperature and carried out the heat treatment first time in 6 hours with 2 ℃/min, then be warming up to 700 ℃ and constant temperature and carried out clinkering in 16 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.The ESEM (SEM) of institute's prepared material shows that its pattern is an elliposoidal, and structure XRD figure spectrum is similar to the collection of illustrative plates of embodiment 2, and layer structural development is good, and the free from admixture peak occurs.
Example 5
This example is to positive electrode active materials LiNi
0.4Co
0.1Mn
0.4Al
0.05Fe
0.05O
2(b+c=0.5) preparation and performance structure test specifically describe.
After 10 moles in nitrate getting nickel (Ni), cobalt (Co) in 4: 1 in molar ratio respectively is made into the 2.5M aqueous solution, under continuous stirring condition, slowly add the pH value of preparing by ammoniacal liquor and ammonium nitrate and be in 10 the cushioning liquid, make nickel cobalt ammonia mixing complex solution 10L, under continuous stirring state, with itself and 10L, 2.4M the NaOH mixed aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 10.5 with the pure NaOH solution of 2.4M, reaction temperature is 60 ℃, and mixing speed is 450rpm.6.5 isolate the Ni-Co complex hydroxide after hour, ageing filter after 2 hours and with behind the distilled water washing several times in 100 ℃ of dryings 9 hours, make presoma after grinding, sieving, accurately measure behind its moisture content and manganese nitrate, aluminum nitrate, ferrous nitrate and monohydrate lithium hydroxide (LiOHH
2O) 1: 0.8: 0.1 in molar ratio: mix grinding was placed in the Based Intelligent Control Muffle furnace in 0.1: 1.06, in dry air, be warming up to 550 ℃ and constant temperature and carried out the heat treatment first time in 2 hours with 5 ℃/min, then be warming up to 760 ℃ and constant temperature and carried out clinkering in 12 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: please refer to Fig. 9, XRD figure spectrum and LiCoO
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.4, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.Please refer to Fig. 8, the SEM collection of illustrative plates shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 5-17 μ m, and the tap density of powder is 2.34g/cm
3See also Figure 10, the chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 187.4932mAh/g, and first discharge specific capacity is 164.6033mAh/g, and coulombic efficiency is 87.79%; Circulating, capability retention is 87.31% after 100 times, and reversible capacity reaches 143.7151mAh/g, and the slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Example 6
This example is to positive electrode active materials LiNi
0.7Co
0.15Mn
0.1Ti
0.03Cu
0.02O
2Preparation and performance structure test specifically describe.
After 10 moles in sulfate getting nickel (Ni), cobalt (Co) in 7: 1.5 in molar ratio respectively is made into the 2.5M aqueous solution, constantly slowly adding under the stirring condition by ammoniacal liquor and ethanedioic acid (H
2C
2O
4) the pH value of preparation is in 10 the cushioning liquid, make nickel cobalt ammonia mixing complex solution 10L, under continuous stirring state, with itself and 10L, 2.6MNaOH mixed aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 11.5 with the pure NaOH solution of 2.6M, reaction temperature is 50 ℃, and mixing speed is 420rpm.Isolate the Ni-Co complex hydroxide after 5 hours, ageing filter after 2 hours and with behind the distilled water washing several times in 80 ℃ of dryings 18 hours, grind, make presoma after sieving, accurately measure behind its moisture content and manganese carbonate, titanium dioxide, copper nitrate and anhydrous nitric acid lithium 1: 0.1176: 0.0353 in molar ratio: mix grinding was placed in the Based Intelligent Control Muffle furnace in 0.02353: 1.06, in dry air, be warming up to 400 ℃ and constant temperature and carried out the heat treatment first time in 3 hours with 5 ℃/min, then be warming up to 750 ℃ and constant temperature and carried out clinkering in 14 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: XRD figure spectrum (not shown) and LiCoO
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.25, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 4-17 μ m, and the tap density of powder is 2.25g/cm
3See also Figure 11, the chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 178.7901mAh/g, and first discharge specific capacity is 147.4936mAh/g, and coulombic efficiency is 85.36%; Circulating, capability retention is 92.17% after 100 times, and reversible capacity reaches 135.9449mAh/g, and the slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Example 7
This example is to positive electrode active materials LiNi
1/3Co
1/3Mn
1/3O
2Preparation and performance structure test specifically describe.
Got 10 moles in the sulfate of nickel (Ni), cobalt (Co) in 1: 1 in molar ratio respectively, after adding water and being made into 2.5M solution, under continuous stirring condition, slowly add the pH value of preparing by ammoniacal liquor and sulfuric acid amine and be in 9.5 the cushioning liquid, make nickel cobalt ammonia mixing complex solution 10L, under continuous stirring state, with itself and 10L, 2.8MNaOH mixed aqueous solution slowly splashes into simultaneously and fills the 7L aqueous solution and regulate in the reactor of its pH value to 11.0 with the pure NaOH solution of 2.8M, reaction temperature is 45 ℃, and mixing speed is 500rpm.5.5 isolate the Ni-Co complex hydroxide after hour, ageing filter after 2 hours and with behind the distilled water washing several times in 120 ℃ of dryings 8 hours, grind, make presoma after sieving, be placed in the Based Intelligent Control Muffle furnace with manganese carbonate and 1: 0.5: 1.06 in molar ratio mix grinding of monohydrate lithium hydroxide after accurately measuring its moisture content, in dry air, be warming up to 450 ℃ and constant temperature and carried out the heat treatment first time in 4 hours with 5 ℃/min, then be warming up to 775 ℃ and constant temperature and carried out clinkering in 16 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result: XRD figure spectrum (not shown) and LiCoO
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.8, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.SEM collection of illustrative plates (not shown) shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 6-14 μ m, and the tap density of powder is 2.21g/cm
3The chemical property of product is tested (not shown) with the little current tester of new prestige to its button cell of making, and material initial charge specific capacity is 210.4795mAh/g, and first discharge specific capacity is 187.9468mAh/g, and coulombic efficiency is 89.29%; Circulating, capability retention is 84.18% after 100 times, and reversible capacity reaches 158.2136mAh/g.The slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Example 8
This example is to positive electrode active materials Li (Ni
1/3Co
1/3Mn
1/3)
0.95Zn
0.02Ca
0.01Ti
0.02O
2Preparation and performance structure test specifically describe.
Got 10 moles in the nitrate of nickel (Ni), cobalt (Co) in 1: 1 in molar ratio respectively, after being made into the 2.5M aqueous solution, under continuous stirring condition, slowly add the pH value of preparing by ammoniacal liquor and diammonium hydrogen phosphate and be in 9 the cushioning liquid, make nickel cobalt ammonia mixing complex solution 10L, under continuous stirring state, itself and 3MNaOH mixed aqueous solution slowly splashed into simultaneously fill the 7L aqueous solution and regulate in the reactor of its pH value to 11.5 with the pure NaOH solution of 3M, reaction temperature is 55 ℃, and mixing speed is 500rpm.Isolate the Ni-Co complex hydroxide after 8 hours, ageing filter after 2 hours and with behind the distilled water washing several times in 80 ℃ of dryings 16 hours, make presoma after grinding, sieving, accurately measure behind its moisture content and manganese nitrate (Mn (NO
3)
2), zinc oxide (ZnO), calcium oxide (CaO), titanium oxide (TiO
2) and monohydrate lithium hydroxide 1: 0.5: 0.03158 in molar ratio: mix grinding was placed in the Based Intelligent Control Muffle furnace in 0.01579: 0.03158: 1.06, in dry air, be warming up to 500 ℃ and constant temperature and carried out the heat treatment first time in 2 hours with 5 ℃/min, then be warming up to 750 ℃ and constant temperature and carried out clinkering in 15 hours with 2 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result (not shown): XRD figure spectrum and LiCoO
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.9, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 5-18 μ m, and the tap density of powder is 2.37g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 211.0247mAh/g, and first discharge specific capacity is 188.7725mAh/g, and coulombic efficiency is 89.46%; Circulating, capability retention is 95.11% after 100 times, and reversible capacity reaches 179.5415mAh/g.The slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Example 9
This example is to positive electrode active materials LiNi
0.8Co
0.1Mn
0.05Al
0.02Cr
0.02Ti
0.01O
2Preparation and performance structure test specifically describe.
Got 10 moles in the sulfate of nickel (Ni), cobalt (Co) in 8: 1 in molar ratio respectively, after adding water and being made into the 2.5M aqueous solution, under continuous stirring condition, slowly add the pH value of preparing by ammoniacal liquor and sulfuric acid amine and be in 11 the cushioning liquid, make nickel cobalt ammonia mixing complex solution 10L, under continuous stirring state, itself and 2.8M NaOH mixed aqueous solution slowly splashed into simultaneously fill the 7L aqueous solution and regulate in the reactor of its pH value to 11 with the pure NaOH solution of 2.8M, reaction temperature is 55 ℃, and mixing speed is 750rpm.8.5 isolate the Ni-Co complex hydroxide after hour, ageing filter after 2 hours and with behind the distilled water washing several times in 110 ℃ of dryings 8 hours, make presoma after grinding, sieving, accurately measure behind its moisture content and manganese carbonate, aluminum nitrate, chromium oxide (CrO), titanium dioxide (TiO
2) and lithium nitrate 1: 0.05556: 0.02222 in molar ratio: mix grinding was placed in the Based Intelligent Control Muffle furnace in 0.02222: 0.01111: 1.06, in dry air, be warming up to 450 ℃ and constant temperature and carried out the heat treatment first time in 4 hours with 3 ℃/min, then be warming up to 750 ℃ and constant temperature and carried out clinkering in 13 hours with 1 ℃/min, then naturally cool to room temperature, grind, sieve and classification after positive electrode active materials.
The structure of present embodiment products therefrom, pattern test result (not shown): XRD figure spectrum and LiCoO
2XRD figure spectrum similar, the peak of I003/I104 is strong than up to more than 1.5, structure peak 006 with 102 and peak 008 and 110 all trend towards the existence of independent peak, thereby can think that synthetic product has layer structure and the crystal formation growth is fine, structural integrity, defective is few.The SEM collection of illustrative plates shows that the grain shape of synthetic product is an elliposoidal, and size is than homogeneous, and average grain diameter is 7-14 μ m, and the tap density of powder is 2.19g/cm
3The chemical property of product is tested its button cell made from the little current tester of new prestige, and material initial charge specific capacity is 181.7728mAh/g, and first discharge specific capacity is 169.3186mAh/g, and coulombic efficiency is 93.15%; Circulating, capability retention is 81.07% after 100 times, and reversible capacity reaches 137.2666mAh/g.The slurrying of pole piece, the processing behavior of filming are good, and slurry is placed after 48 hours and gelatin phenomenon all do not occurred, and the material phenomenon does not appear falling in the pole piece smooth surface of making.
Claims (10)
1, general formula is that the preparation method of the lithium complex metal oxide of formula (I) mainly may further comprise the steps:
Li
a(Ni
bCo
c)M
1-b-cO
2 (I)
A=0.97-1.07 wherein, 0≤b≤1,0≤c≤1,0.5≤b+c≤1
(a) complex solution that mixes of preparation nickel and/or cobalt and ammonia;
(b) will mix ammino and close in solution and the slow simultaneously adding reactor of aqueous slkali, co-precipitation generates nickel and/or cobalt complex hydroxide, makes presoma after ageing, separation, washing, drying;
(c) presoma that (b) step is made and lithium hydroxide or lithium salts and metal M salt or its element source oxide carry out mix grinding;
(d) in 150-550 ℃ of this mixture of following heat treatment, and;
(e) product of gained makes described lithium complex metal oxide in 650-850 ℃ of following heat treatment step (d).
2, the preparation method of lithium complex metal oxide according to claim 1 is characterized in that: described step (a) is to be prepared in ammoniacal liquor cushioning liquid and formed and mix complex solution by nickel and/or cobalt salt.
3, the preparation method of lithium complex metal oxide according to claim 2, it is characterized in that: mixing the preparation environment that ammino closes solution in the described step (a) is the cushioning liquid that the pH value equals 8-11, and cushioning liquid is made up of ammoniacal liquor and amine salt or ammoniacal liquor and weak acid.
4, the preparation method of lithium complex metal oxide according to claim 2 is characterized in that: the saline solution concentration of described step (a) is 0.5-4mol/L, and the 0.5-3 that the middle concentration of lye of step (b) is described saline solution concentration doubly.
5, the preparation method of lithium complex metal oxide according to claim 1, it is characterized in that: the temperature of coprecipitation reaction is 40-80 ℃ in the described step (b), the mixing speed of blender is 200-1000 rev/min during reaction, and the time of coprecipitation reaction is 4-10 hour; Described digestion time was at least 1 hour; Described alkali lye is at least a among NaOH, KOH or the LiOH, and the pH value of solution is 10～12 during reaction.
6, the preparation method of lithium complex metal oxide according to claim 1 is characterized in that: drying is meant that at baking temperature be 60-120 ℃ of dry nickel and/or a cobalt complex hydroxide material 8-36 hour down in the described step (b).
7, the preparation method of lithium complex metal oxide according to claim 1 is characterized in that: the metal M salt in the described step (c) comprises at least a in nitrate, carbonate, organic salt or its element source oxide of metal M.
8, the preparation method of lithium complex metal oxide according to claim 1 is characterized in that: the metal M of the metal M salt in the described step (c) is at least a in aluminium, iron, manganese, titanium, copper, calcium, zinc and the chromium.
9, the preparation method of lithium complex metal oxide according to claim 1 is characterized in that: described step (d) heat treatment time is 2-8 hour; Described step (e) heat treatment time is 6-26 hour.
10, the preparation method of lithium complex metal oxide according to claim 1 is characterized in that: described lithium complex metal oxide is LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2, LiNiO
2, LiCoO
2, LiNi
0.5Co
0.5O
2, LiNi
0.4Co
0.1Mn
0.4Al
0.05Fe
0.05O
2, LiNi
1/3Co
1/3Mn
1/3O
2, LiNi
0.7Co
0.15Mn
0.1Ti
0.03Cu
0.02O
2, Li (Ni
1/3Co
1/3Mn
1/3)
0.95Zn
0.02Ca
0.01Ti
0.02O
2, or LiNi
0.8Co
0.1Mn
0.05Al
0.02Cr
0.02Ti
0.01O
2, wherein prepare LiNi
0.75Co
0.1Al
0.1Mn
0.05O
2Be in step (b), will mix ammino to close solution and aqueous slkali and aluminum salt solution and slowly add in the reactor simultaneously and carry out coprecipitation reaction.
Priority Applications (1)
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