CN1271185A - Preparation method and equipment of the anode material for lithium ion cell - Google Patents
Preparation method and equipment of the anode material for lithium ion cell Download PDFInfo
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- CN1271185A CN1271185A CN00107325A CN00107325A CN1271185A CN 1271185 A CN1271185 A CN 1271185A CN 00107325 A CN00107325 A CN 00107325A CN 00107325 A CN00107325 A CN 00107325A CN 1271185 A CN1271185 A CN 1271185A
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- lithium
- reactor
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- anode material
- cobalt
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 239000010405 anode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 6
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 239000003513 alkali Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims description 31
- 159000000002 lithium salts Chemical class 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910015645 LiMn Inorganic materials 0.000 claims description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000347 yttrium sulfate Inorganic materials 0.000 claims description 2
- 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 description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000009388 chemical precipitation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 2
- 229910003005 LiNiO2 Inorganic materials 0.000 abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract 2
- 229910052744 lithium Inorganic materials 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 17
- 150000001868 cobalt Chemical class 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 150000002815 nickel Chemical class 0.000 description 7
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 6
- 150000002696 manganese Chemical class 0.000 description 6
- CPABIEPZXNOLSD-UHFFFAOYSA-N lithium;oxomanganese Chemical compound [Li].[Mn]=O CPABIEPZXNOLSD-UHFFFAOYSA-N 0.000 description 5
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000320 mechanical mixture Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000002258 gallium Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003746 yttrium Chemical class 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
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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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Compound crystal is first prepared with the atomized, hydrolyzed and deposited lithium or the doped lithium and the carbonate and/or the hydroxide of Co, T, or Mn. The compound crystal is then thermolyzed graidently in stable temperature sections and in oxidant atmosphere into LiCoO2, LiNiO2 or LiMn2O4 or doped LiCoO2, LiNiO2 or LiMn2O4. The adnode material, compared with that prepared through available process, has reasonable crystallite size, high electrochemical activity and stable crystal type and is an ideal anode material for lithium ion cell.
Description
The present invention relates to a kind of manufacturing method and apparatus of anode material for lithium-ion batteries.Specifically a kind of method and apparatus of making high performance lithium ion battery anode material.
The lithium ion anode material of commercialization has lithium cobalt oxygen (LiCoO
2), lithium nickel oxygen (LiNiO
2), lithium manganese oxygen (LiMn
2O
4) wait severally, they are positive active materials of lithium ion chargeable battery, its performance directly determines the capacity and the serviceability of lithium ion chargeable battery.Since initial stage, countries in the world center on synthesizes them, and improves its performance and carried out big quantity research, studies carefully its manufacture method and mainly contains two classes from the nineties:
One class is the solid phase thermal synthesis method, and with their carbonate or with their hydroxide, or with their oxide, by the stoichiometric ratio mechanical mixture, at high temperature calcination forms then.Adopting LiOH and CoO as Sony corporation of Japan is that raw material is made LiCoO 700 ℃ of calcinations
2, Gumman etc. adopt Li
2CO
3, CoCO
3Be raw material, at 400 ℃ of synthetic LiCoO
2, human LiOHH such as Japanese Shuji Yamada
2O and Ni (OH)
2By Li/Ni=1: 1 carries out mechanical mixture, then at 500 ℃-900 ℃ preparation LiNiO down
2
The characteristics of these class methods are to decompose to synthesize positive electrodes such as lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen by elevated temperature heat, and method is simple, and flow process is short.Phenomenons such as shortcoming is that these class methods are to use solid material, through at high temperature coming sintetics by solid-state diffusion between particle and particle after the mechanical mixture, therefore, can not evenly mix, and synthetic product exists crystal formation irregular, and particle characteristics is not good.Because adopt the characteristic of the synthetic product of these class methods such as the particle characteristics that particle size distribution, purity and proportion etc. depend on raw material itself, the particle size of raw material, distribution, proportion and purity have determined characteristics such as the particle size distribution, proportion of final products, so the granularity of product and performance can not be stablized control, random big, most cases is that particle size distribution is wide, proportion is little, electrochemistry capacitance is low, the product homogeneity is poor.
Another kind of is liquid phase synthesizing method, and people such as R.Yazami have studied a kind of low-temperature synthetic method.Under brute force stirs, cobalt acetate suspension is added in the lithium acetate solution, to handle at least 2 hours down at 550 ℃ then, resultant material has the monodisperse particles shape, bigger serface, good crystallization and being made up of stoichiometric proportion.
Chapter good fortune equality people is by measuring Li (NO
3) and Co (NO
3)
26H
2The O mixing adds an amount of tartaric acid, transfers PH=6-8 with ammoniacal liquor, and 900 ℃ of heating got hard grey black LiCoO in 27 hours
2
Mix non-uniform phenomenon though these class methods have changed at high temperature between solid phase particles and particle, but still the end provides reliable mode to control the crystalline condition of reactant in solution system, still can not make uniform particle diameter, the positive electrode of perfect crystalline.
The objective of the invention is to improve the shortcoming of existing method, propose a kind ofly to prepare the homogeneity isomorphous, have the internal crystallization defective, homogeneous grain diameter, than the method and the device of the positive electrode great, that purity is high, specific discharge capacity is big.Further aim of the present invention is to provide a kind of equipment that is used for above-mentioned preparation method.
The present invention can realize with the following method.
One, water-soluble solution and the alkali reaction by lithium salt solution and cobalt or nickel or manganese generates lithium cobalt or the carbonate of lithium nickel or lithium manganese and/or the composite crystal of oxyhydroxide, and its concrete steps are as follows:
(1) described lithium salts being made into concentration is that the aqueous solution of 20～200 grams per liters is standby, and it is that the aqueous solution of 20～200 grams per liters is standby that the water soluble salt of cobalt or nickel or manganese is made into concentration, and it is that the aqueous solution of 1～15 mol is standby that described alkali is made into concentration;
(2) described Aqueous Lithium Salts, cobalt or the nickel that previous step is prepared suddenly or the manganese aqueous solution and alkali lye are sprayed onto by liquid-jet device and carry out chemical reaction and crystallization in the reactor, wherein:
The hydrojet speed of Aqueous Lithium Salts be 10～200 liters/time, the hydrojet speed of the aqueous solution of cobalt or nickel or manganese be 10～200 liters/time, the hydrojet speed of alkali lye be 5～200 liters/time, the pH value of the liquid in the reactor is 7.0～14.0;
Reaction temperature is 30～70 ℃, and the reaction time is 2～100 hours, stirs in the time of reaction, and mixing speed is 20～120 rev/mins, obtains composite crystal;
(3) described composite crystal is separated with reaction solution;
Two, the described composite crystal that will separate carries out thermal decomposition under oxygen atmosphere, generates LiCoO
2Or LiNiO
2Or LiMn
2O
4Product, its concrete steps are as follows:
(1) 400 ± 10 ℃ of thermal decomposition 20～24 hours;
(2) 700～900 ℃ of thermal decompositions 12～15 hours.
Described lithium salts is lithium sulfate or lithium nitrate; The water soluble compound of described cobalt or nickel or manganese is their sulfate or nitrate: nickel salt is nickelous sulfate or nickel nitrate, and cobalt salt is cobaltous sulfate or cobalt nitrate, and manganese salt is manganese sulfate or manganese nitrate.Described alkali be NaOH or potassium hydroxide and/or ammonium carbonate or carbonic hydroammonium and/a kind of in the ammoniacal liquor or several.
Described lithium salts also can be the lithium salts that is mixed with foreign material, dopant is one or more a water soluble compound of zinc, magnesium, calcium, yttrium, platinum, palladium, rhodium, molybdenum, gallium, indium, gold, lanthanum, ammonium, europium, ytterbium, silver, cobalt, nickel, manganese element, it is made into the aqueous solution and mixes with Aqueous Lithium Salts, and the total concentration of dopant solution is 0.01～10.00% of a described lithium salt solution concentration.The doping elements compound adopts water-soluble salt, add kind and amount can for:
Cobalt salt: 10～20 grams per liters and/or yttrium salt: the 0.5-1.0 grams per liter and/or
Gallium salt: 0.2-1.0 grams per liter and/or manganese salt: the 0.2-1.0 grams per liter and/or
Calcium salt: 3-5 grams per liter and/or magnesium salts: the 0.2-1.0 grams per liter and/or
Nickel salt: the 10-50 grams per liter is disposed at alloy in the lithium salt solution.
Preferably can for:
Cobalt salt: 1.8-2 grams per liter and/or yttrium salt: the 0.5-0.6 grams per liter and/or
Gallium salt: 0.2-0.3 grams per liter and/or calcium salt: the 3-5 grams per liter and/or
Nickel salt: 10-20 grams per liter.
Several reactants of the aqueous solution of described Aqueous Lithium Salts and cobalt or nickel or manganese and alkali are reinforced by high-pressure fog, and atomizing hydrolysis deposition generates described composite crystal, and atomisation pressure is 1～20 kilograms per centimeter
2Preferred 3～5 kilograms per centimeter of described atomisation pressure
2
In course of reaction, the constant concentration of the aqueous solution of described Aqueous Lithium Salts and cobalt or nickel or manganese, described alkali makes solution present required alkalescence for stable its chemical reaction amount that surpasses in reactant liquor.The concentration of described Aqueous Lithium Salts is preferably 70～80 grams per liters, and the concentration of the aqueous solution of cobalt or nickel or manganese is preferably 70～80 grams per liters, and alkali Duos 5～10% than the amount of calculating by the chemistry amount, and preferred many 3～5%.
The reaction time for preparing described composite crystal is preferably 30～76 hours.Reaction in described reactor, preceding 15 hours pH value are 8～10, and back 15 hours, pH value was 10.1～14 or 8～14.
Described alkali can be the mixture of NaOH or potassium hydroxide and ammonium carbonate or carbonic hydroammonium, and both proportionings are ammonium carbonate or carbonic hydroammonium: NaOH or potassium hydroxide are 1: 0.5～10.
When spray reactant liquor in reactor, alkali lye sprays from bottom to top, and other reactant liquor sprays from top to bottom, and the crystal that crystallizes out is discharged by the outlet on the still wall that is higher than the top spray material port of reactor; Stirring in reaction, the liquid on the top of reactor are the axial flow form, and lower liquid is the Radial Flow form.
The gradient thermal decomposition is carried out in thermal decomposition in the presence of aerobic, carried out 20-24 hour at 400 ± 10 ℃, carries out 12-15 hour at 700-900 ℃.Oxygen atmosphere when described composite crystal is carried out thermal decomposition realizes that by logical oxygen in equipment oxygen-supply quantity is 0.5～10M
3/ h is preferably 2～3M
3/ h.
Prepare the used equipment of above-mentioned anode material for lithium-ion batteries, it includes charging spout, reactor, centrifuge and thermal decomposer, and described charging spout connects charge pipe, and described charge pipe feeds in the described reactor, is provided with force (forcing) pump on described charge pipe; Described reactor is a jacketed vessel, the termination of each charge pipe in being located at reactor is provided with shower nozzle, shower nozzle on the described charge pipe one of them (promptly spraying the shower nozzle of alkali lye) places the bottom of reactor, shower nozzle on it upwards, shower nozzle on other charge pipe is located at the top of reactor, shower nozzle on it is downward, and the material outlet of described reactor is located on the wall of charge pipe shower nozzle top, described top, establishes pipeline on the described material outlet and leads in the described centrifuge; Described centrifuge is established discharging opening, connects drive access and is connected with described thermal decomposer.
Described shower nozzle is circular cone shower nozzle or multitube shower nozzle or porous coil pipe.Described blender is made up of blender bar and solid paddle thereon, and the upper and lower of described blender sets firmly two kinds of paddles, and the paddle on described top is oar formula or propeller type, and the paddle of bottom is frame or anchor formula.The preferred top of described blender bar sets firmly the propeller type paddle, and the bottom sets firmly anchor formula paddle.Described thermal decomposer is that horizontal multistage timing temperature control pushes away the boat stove continuously.
In the reaction equipment therefor, lithium salts, alkali lye nickel salt or cobalt salt or manganese salt charge door place respectively in the reactor, its best configuration be the reinforced shower nozzle of alkali lye in reactor below, other reinforced shower nozzle is above reactor.
When producing positive electrodes such as high-performance lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, raw material lithium salts, cobalt salt or nickel salt or manganese salt and alkali lye are respectively charged into charging spout, send into after the pressurization in the reactor with chuck heating respectively and react, product is separated and washing through centrifuge, product is put into the horizontal boat stove thermal decomposition that pushes away afterwards, obtains product lithium cobalt oxygen or lithium nickel oxygen or lithium manganese oxygen at last.
The raw materials atomisation pressure is a 1-10 kg/cm 2, and optimum pressure is the 3-5 kg/cm.Reaction should be controlled a stable pH value, is 8-10 in preceding 15 hours control pH value scopes of reacting, back 15 hours, the control pH value is chosen as 10.1-14 or 8-14, and these 30 hours was first reaction time, afterwards, the pH value control numerical value that repeated for first reaction time ...Reactant retained in reactor 30-76 hour.
The present invention compares with existing method, have following advantage: the one, the coated complex chemical compound crystal of generation lithium cobalt or lithium nickel or lithium manganese, the homogeneity isomorphous, highly even, and have huge inside pore volume, particularly when using two kinds or above alkali, can form composite crystal, as when alkali uses NaOH and carbonic hydroammonium, the compound crystal thing that generates is the composite junction crystal of hydroxide and carbonate, component distributing height homogeneous; The 2nd, adopt the atomized water forming solution, make reaction raw materials add in the reactor equably by spraying, upwards spraying the alkali lye mist down and add the alkali shower nozzle, other raw material is sprayed downwards, more make in the crystallization process various raw materials uniform, simultaneously can pass through the conditioned reaction parameter, as pH value, reaction temperature, reaction time wait the particle size distribution homogeneous that guarantees crystalline solid, than great.The 3rd, during the gradient temperature decomposition at high temperature of composite junction crystal, because the carbonate resolution characteristic different with hydroxide makes catabolite have lattice defect and huge inside pore volume, thereby have bigger specific area and the capacitance of Geng Gao.The performance parameter of the positive electrode that makes with the method can be referring to Fig. 3.
Know the needed quality products of the present just international and domestic lithium ion battery of positive electrode such as the lithium cobalt oxygen that the present invention synthesizes from Fig. 3.
The invention will be further described below by embodiment and accompanying drawing.
The drawing of accompanying drawing of the present invention is described as follows:
Fig. 1 is a reaction unit schematic flow sheet of the present invention;
Fig. 2 is the electron-microscope scanning of 1000 times of the amplifications of product of the present invention;
Fig. 3 is the performance table of the lithium ion anode material prepared with method and apparatus provided by the invention.
Below in conjunction with accompanying drawing the embodiment of the invention is described:
The manufacturing process of positive electrode and equipment major technique are with lithium salt solution or contain the lithium salt solution of alloy and cobalt salt or manganese salt or nickel salt and aqueous slkali spray in the reactor of forcing to stir 3 through ejiction opening, at stable pH value, under the uniform temperature, the atomizing hydrolysis forms the composite crystal particle, by regulating alkali lye atomizing hydrolysis rate, make composite crystal generate the particle of 3-8 micron, narrow range and distribution are rationally, when reaching high packed density, also controlled the planform of composite junction crystal, promptly generate and have blemish, internal crystal framework defective and particle endoporus make product have high specific surface and activity.
One embodiment is, will be as the criterion with total solution amount with 50-60 ℃ pure water by alloy earlier is mixed with: yttrium sulfate: 0.5 ± 0.1 grams per liter, gallium sulfate: the lithium sulfate solution of 0.3 ± 0.1 grams per liter.Lithium sulfate concentration be 80 ± 2 grams per liters also with the preparation of 50-60 ℃ pure water, above-mentioned alloy solution is mixed with lithium sulfate solution, the hydrojet speed that is mixed with the lithium sulfate solution of alloy elect as 50 liters/time; Cobalt sulfate solution concentration is 80 ± 2 grams per liters, also with the preparation of 50-60 ℃ pure water, hydrojet speed select 50 liters/time; Alkali lye is the mixture solution of NaOH and carbonic hydroammonium, wherein naoh concentration is 2 mol, carbonic hydroammonium concentration 2 mol, the hydrojet speed of alkali lye is chosen between 5.0-200 liter/time, making preceding 15 hours adjusting pH values in reaction is 9.8 ± 0.1, and be 11.5 ± 0.1 at back 15 hours stable pH values of reaction, reinforced with force (forcing) pump 2, atomisation pressure is 5 kg/cm
2It is 30 hours that reactant RT in reactor 3 is set, and reaction temperature is 55 ± 5 ℃, and heating is again jacket structured in the still because of being reflected at, so the reaction temperature fluctuation is big.Reaction is under agitation carried out, and mixing speed is 70 rev/mins.400 ℃ of thermal decompositions of first section control of thermal decomposition 24 hours, 800 ℃ of thermal decompositions of second section control 15 hours, the molten amount of oxygen is 2M
3/ hour.
As shown in Figure 1, produce the used device of anode material for lithium-ion batteries, constitute by charging spout 1, reactor 3, centrifuge 9 and the horizontal boat stove 10 that pushes away, raw material lithium salts, cobalt salt or nickel salt or manganese salt and alkali lye are respectively charged into charging spout 1, and the optional 1.5 cubic metres of grooves of charging spout are sent in the reactor 3 after force (forcing) pump 2 pressurizations and reacted, reactor 3 optional 2.5 cubic metres, reactor 3 peripheral hardware chucks 4, water or steam control reaction temperature, and be provided with pH value check mouth.The reinforced shower nozzle 5 of alkali lye places the below in the reactor 3, and the reinforced shower nozzle 6 of lithium sulfate and alloy solution and cobalt sulfate solution is located at the top in the still.Charge door circular cone shower nozzle, material sprays through pressure, also can select for use other form shower nozzle or antipriming pipe or porous disc pipe to make aperture and replace circular cone shower nozzle ejection material.Discharging opening 7 is set above the feed(raw material)inlet, and product is overflowed thus, for the time of staying of control reactant, also can establish a plurality of discharging openings 7.Material is through mixing, and reaction can be more even.Reactor 3 centers are equipped with blender, and upper unit propeller 8 ' impels material axially to stir up and down, and the bottom makes the material radial motion for the anchor formula stirs 8.The crystal that crystallizes out is discharged reactor 3 by top discharge mouth 7, product separates and washs, dries through centrifugal separator 9, lithium cobalt oxygen that obtains wetting or lithium nickel oxygen or lithium manganese oxygen, afterwards, product enters horizontal multistage timing temperature control and pushes away 10 thermal decompositions of boat stove continuously, is packaged to be product.Blender 6 in this covering device, centrifuge 9, force (forcing) pump 2 and horizontal multistage regularly temperature control push away boat stove 10 etc. continuously and all have ready-made technology to use for reference, and do not do detailed description.
Fig. 2 is the invention process gained LiCoO
2Product is a layer structure, granularity 3-8 μ m, average grain diameter 5.2 μ m, tap density 2.7 grams per milliliters, electro-chemical activity 156mAh/g.Can think to have crystal defect by the prepared product of the present invention, inside has microcellular structure, and high activity is arranged, and particle size distribution is narrow, big, the stable crystal form of electro-chemical activity, the product that this makes high-capacity lithium ion cell at present just and is pressed for.
Claims (19)
1, a kind of method for preparing anode material for lithium-ion batteries, it is characterized in that: its step is as follows:
One, water-soluble solution and the alkali reaction by lithium salt solution and cobalt or nickel or manganese generates lithium cobalt or the carbonate of lithium nickel or lithium manganese and/or the composite crystal of oxyhydroxide, and its concrete steps are as follows:
(1) described lithium salts being made into concentration is that the aqueous solution of 20～200 grams per liters is standby, it is that the aqueous solution of 20～200 grams per liters is standby that the water soluble salt of cobalt or nickel or manganese is made into concentration, it is that the aqueous solution of 1～15 mol is standby that described alkali is made into concentration, described alkali be NaOH or potassium hydroxide and/or ammonium carbonate or carbonic hydroammonium and/a kind of in the ammoniacal liquor or several;
(2) described Aqueous Lithium Salts, cobalt or the nickel that previous step is prepared suddenly or the manganese aqueous solution and alkali lye carry out chemical reaction and precipitation and crystallization by liquid-jet device with vaporific being sprayed onto in the reactor, wherein:
The hydrojet speed of Aqueous Lithium Salts be 10～200 liters/time, the hydrojet speed of the aqueous solution of cobalt or nickel or manganese be 10～200 liters/time, the hydrojet speed of alkali lye be 5～200 liters/time, the pH value of the liquid in the reactor is 7.0～14.0;
The reaction time temperature is 30～70 ℃, and the reaction time is 2～100 hours, and reaction is stirred simultaneously, and mixing speed is 20～120 rev/mins, obtains composite crystal;
(3) described composite crystal is separated with reaction solution;
Two, the described composite crystal that will separate carries out thermal decomposition under oxygen atmosphere, generates LiCoO
2Or LiNiO
2Or LiMn
2O
4Product, its concrete steps are as follows:
(1) 400 ± 10 ℃ of thermal decomposition 20～24 hours;
(2) 700～900 ℃ of thermal decompositions 12～15 hours.
2, the method for preparing anode material for lithium-ion batteries according to claim 1 is characterized in that: described lithium salts is lithium sulfate or lithium nitrate; The water soluble compound of described cobalt or nickel or manganese is their sulfate or nitrate.
3, the method for preparing anode material for lithium-ion batteries according to claim 1, it is characterized in that: described lithium salts is the lithium salts that is mixed with foreign material, dopant is one or more a water soluble compound of zinc, magnesium, calcium, yttrium, platinum, palladium, rhodium, molybdenum, gallium, indium, gold, lanthanum, ammonium, europium, ytterbium, silver, cobalt, nickel, manganese element, it is made into the aqueous solution and mixes with Aqueous Lithium Salts, and the total concentration of dopant solution is 0.01～10.00% of a described lithium salt solution.
4, the method for preparing anode material for lithium-ion batteries according to claim 1, it is characterized in that: several reactants of the aqueous solution of described Aqueous Lithium Salts and cobalt or nickel or manganese and alkali are reinforced by high-pressure fog, atomizing hydrolysis deposition generates described composite crystal, and atomisation pressure is 1～20 kilograms per centimeter
2
5, the method for preparing anode material for lithium-ion batteries according to claim 4 is characterized in that: described atomisation pressure is 3～5 kilograms per centimeter
2, when spray reactant liquor in reactor, alkali lye sprays from bottom to top, and other reactant liquor sprays from top to bottom, and the crystal that crystallizes out is discharged by the outlet on the still wall that is higher than the top spray material port of reactor; Stirring in reaction, the liquid on the top of reactor are the axial flow form, and lower liquid is the Radial Flow form.
6, the method for preparing anode material for lithium-ion batteries according to claim 1, it is characterized in that: the constant concentration of the aqueous solution of described Aqueous Lithium Salts and cobalt or nickel or manganese, described alkali make solution present required alkalescence for stable its chemical reaction amount that surpasses in reactant liquor.
7, the method for preparing anode material for lithium-ion batteries according to claim 6, it is characterized in that: the concentration of described Aqueous Lithium Salts is 70～80 grams per liters, the concentration of the aqueous solution of cobalt or nickel or manganese is 70～80 grams per liters, and alkali Duos 5～10% than the amount of calculating by the chemistry amount.
8, the method for preparing anode material for lithium-ion batteries according to claim 7 is characterized in that: described alkali is than Duoing 3～5% by stoichiometrical amount.
9, the method for preparing anode material for lithium-ion batteries according to claim 1 is characterized in that: the reaction time for preparing described composite crystal is 30～76 hours.
10, the method for preparing anode material for lithium-ion batteries according to claim 9 is characterized in that: the reaction in described reactor, preceding 15 hours pH value are 8～10, and back 15 hours, pH value was 10.1～14 or 8～14.
11, the method for preparing anode material for lithium-ion batteries according to claim 1 is characterized in that: described alkali is the mixture of NaOH and ammonium carbonate or carbonic hydroammonium, and both proportionings are ammonium carbonate or carbonic hydroammonium: NaOH is 1: 0.5～10.
12, the method for preparing anode material for lithium-ion batteries according to claim 1 is characterized in that: the oxygen atmosphere when described composite crystal is carried out thermal decomposition realizes that by logical oxygen in equipment oxygen-supply quantity is 0.5～10M
3/ h.
13, the method for preparing anode material for lithium-ion batteries according to claim 12 is characterized in that: oxygen-supply quantity is 2～3M
3/ h.
14, the method for preparing anode material for lithium-ion batteries according to claim 1, it is characterized in that: described lithium salts is a lithium sulfate, lithium sulfate is as the criterion with total solution amount with 50～60 ℃ pure water is mixed with the lithium sulfate solution of 80 ± 2 grams per liters, in lithium sulfate solution, also add alloy, be as the criterion with total solution amount with 50～60 ℃ pure water and be mixed with alloy solution, its composition and concentration are: yttrium sulfate 0.5 ± 0.1 grams per liter, gallium sulfate 0.3 ± 0.1 grams per liter, cobaltous sulfate is as the criterion with total solution amount with 50～60 ℃ of pure water and is mixed with the cobalt sulfate solution of 80 ± 2 grams per liters, described alkali is made up of NaOH and carbonic hydroammonium, and concentration is respectively: NaOH 2 mol, carbonic hydroammonium 2 mol; Use force (forcing) pump with 5 kg/cm above-mentioned three kinds of raw materials
2Pressure spray in the reactor, the hydrojet speed of the lithium sulfate of alloy and cobalt sulfate solution be 50 liters/time, the hydrojet speed of alkali lye 5.0～200 liters/time between; Reactant is set to stop in reactor 30 hours, reaction temperature is 55 ± 5 ℃, pH value by solution in the hydrojet speed adjustment reactor of regulating alkali lye in preceding 15 hours of reaction is 9.8 ± 0.1, and the pH value of the solution in back 15 hours in the reactor is 11.5 ± 0.1; Reaction is under agitation carried out, and the rotating speed of blender is 70 rev/mins; The composite crystal that obtains is drawn reactor through centrifugation, and when spray reactant liquor in reactor, alkali lye sprays from bottom to top, and other reactant liquor sprays from top to bottom, and the crystal that crystallizes out is discharged by the outlet on the still wall that is higher than the top spray material port of reactor; Stirring in reaction, the liquid on the top of reactor are the axial flow form, and lower liquid is the Radial Flow form; Then, carry out thermal decomposition again in heating furnace, the phase I of thermal decomposition, the second stage of thermal decomposition was 800 ℃ of heating 15 hours 400 ℃ of heating 24 hours, and the amount that oxygen feeds in the heating furnace is 2M
3/ h.
15, a kind of used equipment of anode material for lithium-ion batteries for preparing, it is characterized in that: include charging spout (1), reactor (3), centrifuge (9) and thermal decomposer (10), described charging spout (1) connects charge pipe, described charge pipe feeds in the described reactor (3), is provided with force (forcing) pump (2) on described charge pipe; Described reactor (3) is a jacketed vessel, the termination of each charge pipe in being located at reactor (3) is provided with shower nozzle (5), one of them places the bottom of reactor shower nozzle on the described charge pipe, shower nozzle on it upwards, shower nozzle on other charge pipe is located at the top of reactor, shower nozzle on it is downward, and the material outlet of described reactor is located on the wall of top of described top charge pipe shower nozzle, establishes pipeline on the described material outlet (7) and leads in the described centrifuge (9); Described centrifuge is established discharging opening, connects drive access and is connected with described thermal decomposer (10), is provided with blender in the reactor.
16, equipment according to claim 15 is characterized in that: described shower nozzle (5) is circular cone shower nozzle or multitube shower nozzle or porous coil pipe.
17, equipment according to claim 15, it is characterized in that: described blender is made up of blender bar and solid paddle thereon, the upper and lower of described blender sets firmly two kinds of paddles, the paddle (8 ') on described top is oar formula or propeller type, and the paddle of bottom (8) is frame or anchor formula.
18, equipment according to claim 17 is characterized in that: described blender bar top sets firmly propeller type paddle (8 '), and the bottom sets firmly anchor formula paddle (8).
19, equipment according to claim 15 is characterized in that: described thermal decomposer is that horizontal multistage timing temperature control pushes away boat stove (10) continuously.
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Date of cancellation: 20130306 Granted publication date: 20040204 Pledgee: China Development Bank Co Pledgor: Shenzhen GEM High-tech Co., Ltd. Registration number: 2007440000405 |
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Denomination of invention: Preparation method and equipment of the anode material for lithium ion cell Effective date of registration: 20130724 Granted publication date: 20040204 Pledgee: China Development Bank Co Pledgor: Shenzhen GEM High-tech Co., Ltd. Registration number: 2013990000502 |
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Address after: 518104, Shenzhen, Guangdong Province, Baoan District, Sha Wu Town, West Industrial Zone, No. 50 Patentee after: Limited company of Green U.S. Address before: 518104, Shenzhen, Guangdong Province, Baoan District, Sha Wu Town, West Industrial Zone, No. 50 Patentee before: Shenzhen GEM High-tech Co., Ltd. |
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