CN105810931A - Gradient-structured multi-element material used for lithium ion batteries - Google Patents
Gradient-structured multi-element material used for lithium ion batteries Download PDFInfo
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- CN105810931A CN105810931A CN201410845856.9A CN201410845856A CN105810931A CN 105810931 A CN105810931 A CN 105810931A CN 201410845856 A CN201410845856 A CN 201410845856A CN 105810931 A CN105810931 A CN 105810931A
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- lithium ion
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- ion battery
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000008859 change Effects 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000008187 granular material Substances 0.000 claims description 15
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000002738 chelating agent Substances 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 239000012266 salt solution Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000004087 circulation Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 229910032387 LiCoO2 Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229940099596 manganese sulfate Drugs 0.000 description 6
- 239000011702 manganese sulphate Substances 0.000 description 6
- 235000007079 manganese sulphate Nutrition 0.000 description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 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 3
- 229910003005 LiNiO2 Inorganic materials 0.000 description 3
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 3
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- 229910013179 LiNixCo1-xO2 Inorganic materials 0.000 description 2
- 229910013171 LiNixCo1−xO2 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229940097267 cobaltous chloride Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- -1 LiOH Chemical class 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910015385 Ni1-a-b(Ni1/2Mn1/2)aCob Inorganic materials 0.000 description 1
- 229910015270 Ni1−a−b(Ni1/2Mn1/2)aCob Inorganic materials 0.000 description 1
- 229910006174 NixCo1−2xMnx Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 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
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a gradient-structured multi-element material used for lithium ion batteries. The composition of the gradient-structured multi-element material is LiNixCoyMnzGdO2, wherein x is not smaller than 0.4 and not greater than 0.9, y+z is not smaller than 0 and not greater than 0.6, d is not smaller than 0 and not greater than 0.1, x+y+z+d is 1, and G is one or more of Li, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, V, Nb, Ta, Mo and W. Components of the above material particle continuously change from inside to outside, and the percentage content of the Ni element on the surface of the material particle is smaller than the percentage content of the Ni element in the material particle. The percentage content X<R> of the Ni element in a position having a distance of R to the center of the material particle is X<0>-aR, wherein X<0> is the percentage content of the Ni element in the center of the material particle, and a is greater than 0. The gradient-structured multi-element material has the advantages of simple preparation technology, low cost and good processing performances, and the lithium ion batteries made of the material have the advantages of small swelling, high capacity, good high-temperature cycle stability and good safety.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, be specifically related to the multicomponent material of a kind of lithium ion battery gradient-structure.
Background technology
Lithium ion battery is more and more extensive in the application of modern society, is currently mainly applied to the fields such as mobile phone, notebook computer, electric tool and electric motor car.The increase to high capacity lithium ion battery demand along with lithium ion battery consumption and electric automobile, has high security, high-energy-density, high power, long circulating, high-environmental and inexpensive lithium ion battery in the urgent need to development.Positive electrode is the key factor of performance and the price determining lithium ion battery, and currently used positive electrode mainly has LiCoO2、LiNiO2、LiNixCo1-xO2、LiNixCoyMn1-x-yO2、LiMn2O4、LiFePO4。LiCoO2Being the positive electrode used by initial lithium ion battery commercialization, and be still currently used main positive electrode, this is primarily due to its stable performance, it is easy to synthesis；But due to Co resource-constrained, this material price is higher, and has certain toxicity, limit its application in some emerging markets.LiNiO2Capacity is high, less costly, but preparation difficulty, the concordance of material property and poor reproducibility, there is comparatively serious safety problem.LiNixCo1-xO2LiNiO can be regarded as2And LiCoO2Solid solution, have LiNiO concurrently2And LiCoO2Advantage, once it is believed that it is most possibly replace LiCoO2Novel anode material, but still suffer from synthesis difficulty, the shortcoming such as safety is poor, combination property haves much room for improvement.There is the LiMn of cubic spinel structure2O4Cost is low, but has that capacity is low, the shortcoming of easy decay.Olivine structural LiFePO4Then there is the shortcoming that voltage is low, capacity is low.
Owing to layer structure is conducive to reversibly intercalation/deintercalation Li+, it is desirable that develop cheaper, more environmentally-friendly, the better Layered Structural Positive Electrode Materials of performance.In recent years, stratiform LiNixCoyMn1-x-yO2Research day by day attracted attention by people, be integrated with LiNiO2、LiCoO2、LiMn2O4Advantage etc. each material: higher capacity, good cyclical stability, high rate capability, heat stability, also there is good cyclical stability at a higher temperature, be the anode material for lithium-ion batteries having very much Development volue.
LiNixCoyMn1-x-yO2In solid solution, the increase of Ni content can improve specific capacity, but the cycle performance of material, security performance decline to some extent.Such as LiNi0.8Co0.1Mn0.1O2Reversible capacity can reach about 190mAh/g, considerably beyond LiCoO2(about 145mAh/g).But, due to problems with, such nickel-rich positive pole material is somewhat prohibitive in its actual application aspect:
First, the violent phase transformation of crystal structure the change of adjoint volume can be there is in nickel-rich positive pole material in the charge/discharge process repeated, the local collapse in crystal layer space can be caused, cause Lithium-ion embeding/deviate from and may be obstructed and cause polarization resistance to increase, thus causing the decline of charge/discharge capabilities.In order to prevent problems, traditional prior art attempts to prepare nickel-rich positive pole material by optimum synthesis condition.But, the nickel-rich positive pole material being prepared out, in charged state, the phase transformation of crystal structure can not be stoped, phase transformation when de-lithium can not be stoped to be heated mutually and decomposition, and the problem causing cycle characteristics severe exacerbation due to recharge/discharge cycles.
Secondly, nickel-rich positive pole material, storing or during circulation, has the problem that excess air produces.Traditional prior art, in order to form good crystal structure, is added excessive lithium source in producing nickel-rich positive pole material process, is then carried out heat treatment in oxygen atmosphere.As a result of which it is, LiCO3Remaining between particles as reaction residue with the lithium salts such as LiOH, they decompose or react with electrolyte and produce CO when charging2Gas, it is possible to cause the generation of cell expansion and the deterioration of high temperature safety.
It is Li that patent application CN1778003 proposes composition formulay(NixCo1-2xMnx)O2, wherein 0.025≤x≤0.5, nickel content is relatively low, and cycle performance is better, and security performance improves to some extent, but specific capacity is relatively low；It is Li that patent application CN101300696 then proposes composition formulax(Ni1-a-b(Ni1/2Mn1/2)aCobAk)yO2, 0.4≤Ni≤0.7,0.1≤Co≤0.4,0.05≤Mn≤0.6, nickel content, specific capacity increase, but the relatively low nickel material of cycle performance, security performance decreases, it is impossible to optimized solution the problems referred to above.
Summary of the invention
The multicomponent material of a kind of lithium ion battery gradient-structure that it is an object of the present invention to provide, this material is high for capacity of lithium ion battery, improves its high temperature circulation stability and security performance simultaneously, and battery tympanites is little, relative inexpensiveness.
For achieving the above object, the invention discloses the multicomponent material of a kind of lithium ion battery gradient-structure, it is composition such as following formula I on average:
LiNixCoyMnzGdO2(Ⅰ)
Wherein, 0.4≤x≤0.9,0≤y+z≤0.6,0≤d≤0.1, x+y+z+d=1, G is one or more elements in Li, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, V, Nb, Ta, Mo, W；
Further, from inside to outside, component continues to change material granule, and the degree of material granule surface Ni element is less than inside material granule.
The multicomponent material of above-mentioned lithium ion battery gradient-structure, described multicomponent material is subglobose multicomponent material granule.
The multicomponent material of above-mentioned lithium ion battery gradient-structure, it is preferred that from inside to outside, Ni element percentage content is linearly gradually lowered described multicomponent material granule, the degree apart from the Ni element that granular center is R place is similar to and meets XR=X0-aR, wherein X0For material granule center Ni element mole percent level, a > 0.
The multicomponent material of above-mentioned lithium ion battery gradient-structure, its meso-position radius is 3 ~ 25um, and tap density is 1.5 ~ 3.0g/cm3。
The multicomponent material of above-mentioned lithium ion battery gradient-structure becomes pole piece with carbon black, Kynoar (PVDF) by 94%:3%:3% weight ratio dispensing slurry, negative pole adopts Delanium, after centre adds membrane winding fluid injection, it is processed into 053048 shell with square aluminum battery；The chemical property of test battery and security performance.(according to lithium ion standard GB/T/T18287-2000:C5Being rated capacity, represent and be discharged to, with 5 hour rates, the electricity that final voltage should provide, unit is Ah or mAh；1C5A charge and discharge cycles refers under 20 ± 5 DEG C of conditions, with 1C5A charges to 4.2V, turns constant-voltage charge to charging current≤0.01C5A, then with 1C5A is discharged to 2.75V, forms 1 cycle, repeats 1C afterwards5A charge/discharge process.1C5A high temperature charge and discharge cycles refers under 60 ± 2 DEG C of conditions, with 1C5A charges to 4.2V, turns constant-voltage charge to charging current≤0.01C5A, then with 1C5A is discharged to 2.75V, forms 1 cycle, repeats 1C afterwards5A charge/discharge process.Specific discharge capacity refers to 0.2C5During A discharge and recharge, the capacity of every gram of positive electrode release under discharge condition, unit is mAh/g;85 DEG C of high temperature storage cell thickness rates of change refer under 20 ± 5 DEG C of conditions, with 0.2C5A charges to 4.2V, turns constant-voltage charge to charging current≤0.01C5A, then with 1C5A is discharged to 2.75V, forms 1 cycle, carries out 1C afterwards5A charge/discharge cycle, when the charged state of circulating battery to the 3rd time circulation, takes off its original depth of battery measurement, then it is placed 4 hours under 85 ± 5 DEG C of conditions, measure its thickness, calculate the thickness change of battery；Thermal shock in 150 DEG C of hot tank refers under 20 ± 5 DEG C of conditions, with 0.2C5A charges to 4.2V, turns constant-voltage charge to charging current≤0.01C5A, then with 1C5A is discharged to 2.75V, forms 1 cycle, carries out 1C afterwards5A charge/discharge cycle, when the charged state of circulating battery to the 3rd time circulation, takes off battery and is placed in baking oven, rise to 150 DEG C with the programming rate of 5 DEG C/min, investigate the time that battery explodes at 150 DEG C.)
The multicomponent material of the lithium ion battery gradient-structure that disclosed in this invention, from the performance of material, take into full account the characteristic of nickel, cobalt, manganese and other element, rational in infrastructure, the height ratio capacity advantage of material can be played, improve high temperature cyclic performance and the security performance of material.Multicomponent material good processability, is fabricated to battery tympanites little.
Specific embodiment
Embodiment 1
The multicomponent material of a kind of lithium ion battery gradient-structure, consists of LiNi0.6Co0.20Mn0.2O2, material granule center Ni element mole percent level is 100%, and Ni constituent content is gradually lowered from inside to outside.Granule is spherical, and meso-position radius is 15.3um, and tap density is 2.55g/cm3。
Preparation method is as follows:
nullThe nickel sulfate solution 300L of preparation 1.5mol/L，The cobalt sulfate solution 100L of 1.5mol/L，The manganese sulfate solution 100L of 1.5mol/L，The chelating agent ammonia spirit of 5.0mol/L，The precipitant sodium hydroxide solution of 8mol/L，The nickel sulfate solution of 1.5mol/L is put in the container A with stirring，By the cobalt sulfate solution of 1.5mol/L，The manganese sulfate solution of 1.5mol/L joins in container A with 3.4L/h flow velocity respectively，Container A solution simultaneously、Chelating agent、Precipitant also flows in the reaction vessel adding stirring，React and carry out under nitrogen atmosphere is protected，Control the pH value of solution of reaction system 11.3，Water bath heating temperature is 50 DEG C，The mol ratio of chelating agent ammonia and the total salt of metal is 1.0，Response time 30h.By material filtering, washing, drying after reaction, obtain multicomponent material presoma.This presoma and Lithium hydrate are sufficiently mixed with 1:1.05 mol ratio, under air atmosphere, 890 DEG C of insulation 10h.Temperature fall, after pulverizing, sieving, obtains the multicomponent material of spherical gradient structure.
After tested, the meso-position radius of this material is 15.3um, tap density 2.55g/cm3, specific discharge capacity is 172mAh/g, room temperature 1C5100 capability retentions 93% of A charge and discharge cycles, 100 weeks capability retentions 87% of 60 DEG C of circulations, after 85 ± 2 DEG C of high temperature storage 4h, cell thickness rate of increase is 7.3%, and the thermal shock test result in 150 DEG C of hot tank is within 60 minutes, do not explode, do not ftracture.
Embodiment 2
The multicomponent material of a kind of lithium ion battery gradient-structure, consists of LiNi0.75Co0.15Mn0.05Al0.05O2, material granule center Ni element mole percent level is 85%, and Ni constituent content is gradually lowered from inside to outside.Granule is spherical, and meso-position radius is 10.1um, and tap density is 2.45g/cm3
Preparation method is as follows:
Nickel dichloride., cobaltous chloride, manganese chloride are dissolved mixing salt solution (1) 500L obtaining 2mol/L according to the metal molar ratio than 0.85:0.1:0.05, cobalt nitrate, manganese sulfate, aluminum nitrate are dissolved mixing salt solution (2) 66.5L obtaining 2mol/L according to the metal molar ratio than 0.52:0.05:0.43, the chelating agent ammonium sulfate of preparation 2mol/L, the mol ratio of chelating agent and the total salt of metal is 0.7；The precipitant potassium hydroxide solution of preparation 5mol/L; controlling precipitant with the total salt mol ratio of metal is 2.0; mixing salt solution (1) is put in the container A with stirring; the mixing salt solution (2) of 2mol/L is joined in container A with 3.33L/h flow velocity; simultaneously container A solution, chelating agent, precipitant flow in the reaction vessel adding stirring; react and carry out under nitrogen atmosphere is protected; control the pH value of solution of reaction system 11.5; water bath heating temperature is 60 DEG C, response time 20h.By material filtering, washing, drying after reaction, obtain multicomponent material presoma.This presoma and lithium carbonate are sufficiently mixed with 1:0.52 mol ratio, under air atmosphere, 930 DEG C of insulation 15h.Temperature fall, after pulverizing, sieving, obtains the multicomponent material of spherical gradient structure.
After tested, the meso-position radius of this material is 10.1um, tap density 2.45g/cm3, specific discharge capacity is 176mAh/g, room temperature 1C5100 capability retentions 92% of A charge and discharge cycles, 100 weeks capability retentions 86% of 60 DEG C of circulations, after 85 ± 2 DEG C of high temperature storage 4h, cell thickness rate of increase is 8.6%, and the thermal shock test result in 150 DEG C of hot tank is within 60 minutes, do not explode, do not ftracture.
Embodiment 3
The multicomponent material of a kind of lithium ion battery gradient-structure, consists of LiNi0.50Co0.25Mn0.20Al0.04Mg0.01O2, material granule center Ni element mole percent level is 80%, and Ni constituent content is gradually lowered from inside to outside.Granule is spherical, and meso-position radius is 9.9um, and tap density is 2.46g/cm3。
Preparation method is as follows:
Nickel nitrate, cobalt nitrate, manganese chloride are dissolved mixing salt solution (1) 1111L obtaining 1.8mol/L according to the metal molar ratio than 0.8:0.1:0.1, cobaltous chloride, manganese sulfate, aluminum nitrate, magnesium chloride are dissolved mixing salt solution (2) 667L obtaining 1.8mol/L according to the metal molar ratio than 0.5:0.366:0.107:0.027, the chelating agent ammonia spirit of preparation 10mol/L, the mol ratio of chelating agent and the total salt of metal is 0.8；The precipitant sodium hydroxide solution of preparation 8mol/L; controlling precipitant with the total salt mol ratio of metal is 2.05; mixing salt solution (1) is put in the container A with stirring; mixing salt solution (2) is joined in container A with 26.7L/h flow velocity; simultaneously container A solution, chelating agent, precipitant flow in the reaction vessel adding stirring, reacts and carries out under nitrogen atmosphere is protected, control the pH value of solution of reaction system 11.5; water bath heating temperature is 55 DEG C, response time 25h.By material filtering, washing, drying after reaction, obtain multicomponent material presoma.This presoma and lithium carbonate are sufficiently mixed with 1:0.525 mol ratio, under air atmosphere, 850 DEG C of insulation 16h.Temperature fall, after pulverizing, sieving, obtains the multicomponent material of spherical gradient structure.
After tested, the meso-position radius of this material is 9.9um, tap density 2.46g/cm3, specific discharge capacity is 158mAh/g, room temperature 1C5100 capability retentions 94% of A charge and discharge cycles, 100 weeks capability retentions 88% of 60 DEG C of circulations, after 85 ± 2 DEG C of high temperature storage 4h, cell thickness rate of increase is 5.9%, and the thermal shock test result in 150 DEG C of hot tank is within 60 minutes, do not explode, do not ftracture.
Embodiment 4
The multicomponent material of a kind of lithium ion battery gradient-structure, consists of LiNi0.672Co0.144Mn0.144Al0.02Mg0.02O2, material granule center Ni element mole percent level is 70%, and Ni constituent content is gradually lowered from inside to outside.Granule is spherical, and meso-position radius is 6.6um, and tap density is 2.41g/cm3。
Preparation method is as follows:
Nickel dichloride., cobaltous sulfate, manganese sulfate are dissolved mixing salt solution (1) 250L obtaining 2mol/L according to the metal molar ratio than 0.7:0.15:0.15, aluminum sulfate, magnesium sulfate are dissolved mixing salt solution (2) 10.5L obtaining 2mol/L according to the metal molar ratio than 0.5:0.5, the chelating agent ammonia spirit of preparation 12mol/L, the mol ratio of chelating agent and the total salt of metal is 0.9；The precipitant potassium hydroxide solution of preparation 6mol/L; controlling precipitant with the total salt mol ratio of metal is 2.10; mixing salt solution (1) is put in the container A with stirring; mixing salt solution (2) is joined in container A with 0.7L/h flow velocity; simultaneously container A solution, chelating agent, precipitant flow in the reaction vessel adding stirring, reacts and carries out under nitrogen atmosphere is protected, control the pH value of solution of reaction system 12.4; water bath heating temperature is 60 DEG C, response time 15h.By material filtering, washing, drying after reaction, obtain multicomponent material presoma.This presoma and lithium nitrate are sufficiently mixed with 1:1.03 mol ratio, under oxygen atmosphere, 840 DEG C of insulation 12h.Temperature fall, after pulverizing, sieving, obtains the multicomponent material of spherical gradient structure.
After tested, the meso-position radius of this material is 6.6um, tap density 2.41g/cm3, specific discharge capacity is 175mAh/g, room temperature 1C5100 capability retentions 92% of A charge and discharge cycles, 100 weeks capability retentions 86% of 60 DEG C of circulations, after 85 ± 2 DEG C of high temperature storage 4h, cell thickness rate of increase is 7.9%, and the thermal shock test result in 150 DEG C of hot tank is within 60 minutes, do not explode, do not ftracture.
Embodiment 5
The multicomponent material of a kind of lithium ion battery gradient-structure, consists of LiNi0.8Co0.075Mn0.075Al0.02Mg0.02Y0.01O2, material granule center Ni element mole percent level is 100%, and Ni constituent content is gradually lowered from inside to outside.Granule is spherical, and meso-position radius is 24.2um, and tap density is 2.75g/cm3。
Preparation method is as follows:
Nickel sulfate solution (1) 667L of preparation 1.5mol/L, cobaltous sulfate, manganese sulfate, aluminum nitrate, magnesium sulfate, Yttrium trinitrate are dissolved mixing salt solution (2) 167L obtaining 1.5mol/L according to the metal molar ratio than 0.375:0.375:0.1:0.1:0.05, the chelating agent ammonia spirit of preparation 5mol/L, the mol ratio of chelating agent and the total salt of metal is 0.95；The precipitant sodium hydroxide solution of preparation 8mol/L; controlling precipitant with the total salt mol ratio of metal is 1.95; nickel sulfate solution (1) is put in the container A with stirring; mixing salt solution (2) is joined in container A with 4.2L/h flow velocity; simultaneously container A solution, chelating agent, precipitant flow in the reaction vessel adding stirring, reacts and carries out under nitrogen atmosphere is protected, control the pH value of solution of reaction system 11.6; water bath heating temperature is 50 DEG C, response time 40h.By material filtering, washing, drying after reaction, obtain multicomponent material presoma.This presoma and Lithium hydrate are sufficiently mixed with 1:1.04 mol ratio, under oxygen atmosphere, 830 DEG C of insulation 15h.Temperature fall, after pulverizing, sieving, obtains the multicomponent material of spherical gradient structure.
After tested, the meso-position radius of this material is 24.2um, tap density 2.75g/cm3, specific discharge capacity is 186mAh/g, room temperature 1C5100 capability retentions 91% of A charge and discharge cycles, 100 weeks capability retentions 85% of 60 DEG C of circulations, after 85 ± 2 DEG C of high temperature storage 4h, cell thickness rate of increase is 9.2%, and the thermal shock test result in 150 DEG C of hot tank is within 60 minutes, do not explode, do not ftracture.
Except above example, all the other amendment carried out with doctrine of equivalents, interpolation and replacements all should within scope of the presently claimed invention.
Claims (3)
1. a multicomponent material for lithium ion battery gradient-structure, its average formula I composed as follows:
LiNixCoyMnzGdO2(Ⅰ)
Wherein, 0.4≤x≤0.9,0≤y+z≤0.6,0≤d≤0.1, x+y+z+d=1, G is one or more elements in Li, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, V, Nb, Ta, Mo, W；
Further, from inside to outside, component continues to change multicomponent material granule, the mole percent level (Ni/(Ni+Co+Mn+G) of material granule surface Ni element) less than inside material granule.
2. the multicomponent material of lithium ion battery gradient-structure according to claim 1, it is characterized in that described multicomponent material granule from inside to outside, Ni element mole percent level is linearly gradually lowered, and the degree apart from the Ni element that granular center is R place is similar to and meets XR=X0-aR, wherein X0For material granule center Ni element mole percent level, a > 0.
3. the multicomponent material of lithium ion battery gradient-structure according to claim 1 and 2, it is characterised in that described multicomponent material granule is spherical, meso-position radius is 3 ~ 25um, and tap density is 1.5 ~ 3.0g/cm3。
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| CN201410845856.9A CN105810931A (en) | 2014-12-31 | 2014-12-31 | Gradient-structured multi-element material used for lithium ion batteries |
| KR1020177021025A KR20170102293A (en) | 2014-12-31 | 2015-09-30 | Multicomponent materials having a classification structure for lithium ion batteries, a method for manufacturing the same, an anode of a lithium ion battery and a lithium ion battery |
| PCT/CN2015/091179 WO2016107237A1 (en) | 2014-12-31 | 2015-09-30 | Lithium ion battery gradation structure multiple-element material and manufacturing method thereof, and lithium ion battery and anode thereof |
| JP2017553292A JP6612356B2 (en) | 2014-12-31 | 2015-09-30 | Multi-component material having an inclined structure for lithium ion battery, preparation method thereof, positive electrode of lithium ion battery and lithium ion battery |
| CN201580062075.5A CN107004851A (en) | 2014-12-31 | 2015-09-30 | Multicomponent material, its preparation method, lithium ion cell positive and the lithium ion battery of lithium ion battery gradient-structure |
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| CN108649205A (en) * | 2018-05-15 | 2018-10-12 | 哈尔滨工业大学 | A kind of anode material for lithium-ion batteries and its preparation with variable slope concentration gradient doped structure |
| CN109411718A (en) * | 2018-09-28 | 2019-03-01 | 佛山市德方纳米科技有限公司 | The preparation method of the tertiary cathode material of doping vario-property |
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| CN102339984A (en) * | 2010-07-28 | 2012-02-01 | 北京当升材料科技股份有限公司 | Preparation method of spherical material with multilayer coating structure |
| CN103904318A (en) * | 2012-12-28 | 2014-07-02 | 惠州比亚迪电池有限公司 | Lithium battery positive electrode material and preparation method thereof |
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| CN102339984A (en) * | 2010-07-28 | 2012-02-01 | 北京当升材料科技股份有限公司 | Preparation method of spherical material with multilayer coating structure |
| CN103904318A (en) * | 2012-12-28 | 2014-07-02 | 惠州比亚迪电池有限公司 | Lithium battery positive electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108649205A (en) * | 2018-05-15 | 2018-10-12 | 哈尔滨工业大学 | A kind of anode material for lithium-ion batteries and its preparation with variable slope concentration gradient doped structure |
| CN109411718A (en) * | 2018-09-28 | 2019-03-01 | 佛山市德方纳米科技有限公司 | The preparation method of the tertiary cathode material of doping vario-property |
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