CN115706229A - Preparation method and application of surface in-situ modified all-solid-state battery high-nickel positive electrode material and lithium ion all-solid-state battery - Google Patents
Preparation method and application of surface in-situ modified all-solid-state battery high-nickel positive electrode material and lithium ion all-solid-state battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 90
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 87
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims description 74
- 239000010416 ion conductor Substances 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 84
- 238000000576 coating method Methods 0.000 claims abstract description 80
- 239000011248 coating agent Substances 0.000 claims abstract description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 229920001690 polydopamine Polymers 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000002052 molecular layer Substances 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960003638 dopamine Drugs 0.000 claims abstract description 22
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 17
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000010406 cathode material Substances 0.000 claims description 49
- 238000000498 ball milling Methods 0.000 claims description 48
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 53
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 66
- 239000000126 substance Substances 0.000 description 19
- 239000011572 manganese Substances 0.000 description 17
- 229910013716 LiNi Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007853 buffer solution Substances 0.000 description 10
- -1 meanwhile Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910010093 LiAlO Inorganic materials 0.000 description 3
- 229910013457 LiZrO Inorganic materials 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004888 barrier function 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
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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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 invention discloses a preparation method of a surface in-situ modified all-solid-state battery high-nickel anode material, which comprises the following steps: firstly, uniformly mixing a high-nickel hydroxide precursor, a lithium source and an additive and sintering to obtain a sintered material; step two, uniformly mixing the ion conductor coating source and the sintering material and then calcining to obtain a lithium ion conductor coating material; dissolving dopamine hydrochloride and tris (hydroxymethyl) aminomethane in methanol to obtain dopamine polymerization coating solution, and adding a lithium ion conductor coating material into the coating solution to obtain mixed dispersion solution; and fourthly, preparing the surface in-situ modified all-solid-state battery high-nickel anode material. The invention also discloses application of the preparation method and a lithium ion all-solid-state battery. According to the invention, the lithium ion conductor layer obtained by reacting residual alkali free lithium on the surface of the sintering material with the ion conductor coating source is utilized, the damage of the surface structure of the anode material is prevented, the mixed arrangement of lithium and nickel is inhibited, and the safety performance of the battery is improved by adopting the polydopamine nano layer.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material, application of the material and a lithium ion all-solid-state battery.
Background
At present, among commercialized cathode materials, a ternary high-nickel cathode material is a mainstream cathode material for lithium ion batteries at present due to the advantages of low macro cost, mature tool equipment, simple preparation process, high specific discharge capacity (more than 200 mAh/g) and the like.
However, the high nickel layered positive electrode material of the conventional lithium ion battery has a problem of poor compatibility with the solid electrolyte. The method specifically comprises the following steps: firstly, the problems of potential mismatching, side reaction, space charge layer effect and the like with the current sulfide-based solid electrolyte are solved; furthermore, the reaction energy of the garnet-type oxide electrolyte lithium lanthanum zirconium oxide (e.g., LLZO) with the fully lithiated layered positive electrode material is zero, but during charging, LLZO reacts with the semi-lithiated positive electrode; secondly, due to the existence of transition metals such as nickel, cobalt and manganese, the organic electrolyte polyethylene oxide (PEO) and the high-nickel layered cathode material can react with each other, so that the usable electrochemical window of the PEO electrolyte is reduced. The problems are all barriers to the application of the high-nickel layered cathode material in the solid-state lithium battery, and the development of the all-solid-state lithium ion battery is severely restricted.
Meanwhile, the high gram capacity of the high-nickel cathode material is improved, and the problem is that the thermal stability of oxygen release is reduced and thermal runaway occurs. Under high temperature and high pressure, the anode material is decomposed, a large amount of oxygen is released to cause the serious reduction of the anode performance, thermal runaway is easily triggered, a large amount of heat and energy are rapidly released, and the safety of the battery is endangered. During the application process of the high-nickel ternary battery, a thermal runaway event occurs, and once the thermal runaway event occurs, serious consequences are caused to the life and property. This further emphasizes the important role of inhibiting oxygen release of high nickel cathode materials in the safety of lithium ion batteries.
The above problems are all obstacles to the application of high nickel layered cathode materials in solid lithium batteries, and the development of all solid lithium ion batteries is severely restricted.
Disclosure of Invention
The invention aims to provide a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material, application thereof and a lithium ion all-solid-state battery aiming at technical defects in the prior art.
Therefore, the invention provides a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material, which comprises the following steps:
step one, uniformly mixing a high-nickel hydroxide precursor, a lithium source and an additive to obtain a mixture, and sintering the mixture to obtain a sintered material;
secondly, uniformly mixing an ion conductor coating source with the sintered material obtained in the first step, and then calcining to obtain a lithium ion conductor coating material with an ion conductor coating layer;
dissolving dopamine hydrochloride and trihydroxymethyl aminomethane in methanol to obtain dopamine polymerization coating liquid, and slowly adding the lithium ion conductor coating material obtained in the second step into the dopamine polymerization coating liquid to obtain mixed dispersion liquid;
and fourthly, stirring the mixed dispersion liquid at room temperature, introducing oxygen into the mixed dispersion liquid to enable the lithium ion conductor coating material to be polymerized and coated on the polydopamine nano layer, and filtering, separating, drying in vacuum and sieving to finally obtain the surface in-situ modified all-solid-state battery high-nickel positive electrode material.
Preferably, in the first step, the additive comprises any one of or a combination of at least two of an oxide, a hydroxide, a carbonate and a nitrate of M';
wherein M' comprises any one or the combination of at least two of Zr, sr, nb, al, Y, W or Mg.
Preferably, in the first step, the sintering temperature is 720-780 ℃, and the sintering time is 9-14 h;
in the first step, the sintering atmosphere is oxygen atmosphere;
in the first step, the mixing mode is specifically that first ball milling is carried out through a first ball milling mixer to realize mixing, so as to obtain ball grinding materials;
the rotating speed of the first ball milling is 300-400 r/min;
the time of the first ball milling is 2-4 h;
the ball milling agent used in the first ball milling comprises ethanol;
in the second step, the calcining temperature is 280-750 ℃ and the time is 8-10 h;
in the second step, the atmosphere of the calcination is air atmosphere;
in the second step, the mixing mode is specifically that the ball milling is carried out for the second time by a second ball milling mixer to realize mixing, so as to obtain the ball grinding material;
the rotating speed of the second ball milling is 100-300 r/min;
the time of the second ball milling is 1-3 h;
the ball milling agent used for the second ball milling comprises ethanol.
Preferably, in the first step, the lithium source includes at least one of lithium hydroxide and lithium carbonate.
Preferably, in the second step, the ion conductor layer is obtained by reacting residual alkali free lithium on the surface of the sintering material with an ion conductor coating source, wherein the addition amount of the ion conductor coating source accounts for 0.8-1.5% of the total mass of the sintering material;
the ion conductor cladding source comprises Nb 2 O 5 、SiO 2 、ZrO 2 、Al 2 O 3 、TiO 2 And H 3 BO 3 At least one of (a).
Preferably, in the third step, the concentration of tris (hydroxymethyl) aminomethane added to the dopamine polymerization coating solution is 0.3 to 0.5mmol/L;
in the third step, the adding concentration of the dopamine hydrochloride in the dopamine polymerization coating solution is 0.1-0.5 mmol/L;
in the mixed dispersion liquid, the mass concentration of the lithium ion conductor coating material was 200g/L.
Preferably, in the fourth step, the stirring time is 13h;
in the fourth step, the rotating speed of stirring is 450r/min;
in the fourth step, the drying temperature is 180 ℃; the drying time is 8h;
in the fourth step, the mesh number of the screen used for the screening was 300 mesh.
In addition, the invention also provides application of the preparation method of the surface in-situ modified all-solid-state battery high-nickel cathode material, which is applied to the high-nickel cathode material of the lithium ion all-solid-state battery.
In addition, the invention also provides a lithium ion all-solid-state battery, which comprises the surface in-situ modified all-solid-state battery high-nickel positive electrode material prepared by the preparation method of the surface in-situ modified all-solid-state battery high-nickel positive electrode material.
Compared with the prior art, the invention provides the preparation method and the application of the surface in-situ modified all-solid-state battery high-nickel positive electrode material and the lithium ion all-solid-state battery, the design is scientific, the damage of the surface structure of the positive electrode material is prevented by utilizing the lithium ion conductor layer obtained by the reaction of residual alkali free lithium on the surface of the sintering material and the ion conductor coating source, the lithium nickel mixed discharge is inhibited, the safety performance of the battery is improved by adopting the polydopamine nano layer, and the method has great practical significance.
The high-nickel anode material directly coats the lithium ion conductor layer and the polydopamine nano layer, changes the surface physical and chemical characteristics of the anode material, and reduces the damage to the surface structure of the anode material and further reduces the mixed discharge of lithium and nickel compared with the high-nickel anode material subjected to the water washing process.
According to the technical scheme, the ion conductor layer is coated in situ by fully utilizing the residual alkali on the surface of the material, so that the electrochemical performance of the anode material is improved by reducing the gas generation of the battery.
The high-nickel anode material provided by the invention has no problem of treatment of alkali-containing industrial wastewater, and is environment-friendly. The lithium ion conductor layer coated by the high-nickel anode material can improve the lithium ion transmission efficiency, and can avoid the occurrence of side reaction caused by the direct contact of the anode material and the solid electrolyte to cause huge interface impedance, thereby prolonging the service life of the all-solid battery;
in addition, the high-nickel anode material provided by the invention coats the poly-dopamine nano layer, and when the anode material releases oxygen during high-voltage charging and discharging, the poly-dopamine nano layer can fix released oxygen radicals, so that the safety of the all-solid-state battery is improved.
Drawings
Fig. 1 is a flow chart of a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material provided by the invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the accompanying drawings and embodiments.
Referring to fig. 1, in order to prepare the surface in-situ modified all-solid-state battery high-nickel positive electrode material, the invention provides a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material, which comprises the following steps:
the method comprises the following steps of firstly, uniformly mixing a high-nickel hydroxide precursor, a lithium source and an additive to obtain a mixture, and then sintering the mixture to obtain a sintered material;
secondly, uniformly mixing an ion conductor coating source with the sintered material obtained in the first step, and then calcining to obtain a lithium ion conductor coating material with an ion conductor coating layer;
dissolving dopamine hydrochloride and trihydroxymethyl aminomethane in methanol to obtain dopamine polymerization coating liquid, and slowly adding the lithium ion conductor coating material obtained in the second step into the dopamine polymerization coating liquid to obtain mixed dispersion liquid;
and fourthly, stirring the mixed dispersion liquid at room temperature, introducing oxygen into the mixed dispersion liquid to enable the lithium ion conductor coating material to be polymerized and coated on the polydopamine nano layer, and filtering, separating, drying in vacuum and sieving to finally obtain the surface in-situ modified all-solid-state battery high-nickel positive electrode material.
It should be noted that the technical principle of the present invention is as follows: the method comprises the steps of preparing a sintering material by taking high-nickel hydroxide, a lithium source and an additive as raw materials through mixing and sintering, adopting an ion conductor to coat the source, and carrying out solid-phase sintering in-situ coating by utilizing surface residual alkali of the sintering material, meanwhile, coating a polydopamine nano-layer through surface wet method in-situ polymerization, and preparing the surface in-situ modified all-solid-state battery high-nickel positive electrode material by adopting twice sintering and twice in-situ coating. The cathode material provided by the invention has the characteristics of improving the performance of the all-solid-state battery and high safety, does not have the problem of treatment of alkali-containing industrial wastewater, and is environment-friendly.
In a first step, embodied, a high nickel hydroxide precursor, which is a ternary cathode material, has the chemical formula Ni x Co y M z (OH) 2 Wherein x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.2, x + y + z =1, and the component M is Mn or Al;
in the first step, specifically, on the basis of the high nickel hydroxide precursor, the mass percent of the lithium source is 41-48% of the high nickel hydroxide precursor, and the mass percent of the additive is 0.05-1% of the high nickel hydroxide precursor.
In the first step, specifically in implementation, the additive, including any one of or a combination of at least two (i.e., at least one) of the oxides, hydroxides, carbonates, and nitrates of M', typical but non-limiting combinations include a combination of metal oxides and metal hydroxides, a combination of metal oxides and metal carbonates, or a combination of metal carbonates and metal nitrates.
Where M' includes any one or a combination of at least two (i.e., at least one) of Zr, sr, nb, al, Y, W, or Mg, typical but non-limiting combinations include combinations of Zr and Sr, zr and Nb, zr and Al, zr and Y, zr and W, or Zr and Mg.
In particular implementations, the dopant (i.e., additive), specifically includes zirconium dioxide (ZrO) 2 ) Strontium carbonate (SrCO) 3 ) Aluminum oxide (Al) 2 O 3 ) Yttrium oxide (Y) 2 O 3 ) Tungsten oxide (WO) 3 ) And magnesium oxide (MgO), the above examples being merely for ease of understanding and not being limiting.
In the first step, the sintering temperature is 720-780 ℃, and the sintering time is 9-14 h. For example, the sintering temperature may be 720 ℃,740 ℃,750 ℃, 760 ℃, 770 ℃ or 780 ℃, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable. For example, the sintering time may be 9h, 10h, 11h, 12h, 13h, 14h, etc., but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In the first step, specifically, the sintering atmosphere is an oxygen atmosphere.
In the first step, specifically, in terms of implementation, the mixing mode is specifically that the first ball milling is carried out through a first ball milling mixer to realize mixing, so as to obtain a ball grinding material;
the rotating speed of the first ball milling is 300-400 r/min, such as 300r/min, 350r/min or 400r/min, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable;
the time of the first ball milling is 2 to 4 hours, for example, 2 hours, 3 hours or 4 hours, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Wherein, the ball milling agent used in the first ball milling comprises ethanol.
In a first step, specifically in implementation, the lithium source includes at least one of lithium hydroxide and lithium carbonate;
in the second step, the temperature of the calcination is 280-750 ℃ and the time is 8-10 h. For example, the temperature of calcination may be 280 ℃, 350 ℃, 450 ℃, 550 ℃, 650 ℃ or 750 ℃, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable. For example, the calcination time may be 8 hours, 9 hours, or 10 hours, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In the second step, specifically, the atmosphere of the calcination is air atmosphere.
In the second step, specifically, in terms of implementation, the mixing mode is specifically that the ball milling is carried out for the second time by a second ball milling mixer, so as to realize mixing, and obtain the ball grinding material;
the rotation speed of the second ball milling is 100-300 r/min, for example, 100r/min, 200r/min or 300r/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The time of the second ball milling is 1 to 3 hours, for example, 1 hour, 2 hours or 3 hours, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Wherein, the ball milling agent used in the second ball milling comprises ethanol.
In the second step, specifically, the ion conductor layer is obtained by reacting residual alkali free lithium on the surface of the sintering material with an ion conductor coating source, wherein the addition amount of the ion conductor coating source accounts for 0.8-1.5% of the total mass of the sintering material, and may be, for example, 0.8wt%, 1wt%, 1.2wt% or 1.5wt%, but is not limited to the recited values, and other unrecited values in the range of the values are also applicable;
in a second step, in particular implementation, the ion conductor cladding source comprises Nb 2 O 5 、SiO 2 、ZrO 2 、Al 2 O 3 、TiO 2 And H 3 BO 3 At least one of (a);
wherein when the ion conductor coating sources are respectively Nb 2 O 5 、SiO 2 、ZrO 2 、Al 2 O 3 、TiO 2 Or H 3 BO 3 In this case, the material in the ion conductor coating layer corresponding to the formed lithium ion conductor coating material is LiNbO, respectively 3 、Li 2 SiO 3 、LiZrO 2 、LiAlO 2 、Li 4 Ti 5 O 12 And Li 3 BO 3 ；
In the third step, specifically, methanol is used as an analytical reagent and used as a solvent, tris (hydroxymethyl) aminomethane is dissolved in methanol (for example, 1L of methanol) to obtain a primary buffer solution with a preparation concentration of 0.3 to 0.5mmol/L, and dopamine hydrochloride is dissolved in the primary buffer solution with a preparation concentration of 0.1 to 0.5mmol/L, so that a dopamine polymerization coating solution is obtained.
In the third step, specifically, the concentration of tris (hydroxymethyl) aminomethane added to the dopamine polymerization coating solution is 0.3 to 0.5mmol/L, preferably 0.3mmol/L, 0.4mmol/L or 0.5mmol/L, but not limited to the recited values, and other values not recited in the numerical range are also applicable;
in the third step, specifically, the dopamine hydrochloride is added to the dopamine polymerization coating solution at a concentration of 0.1 to 0.5mmol/L, for example, 0.1mmol/L, 0.2mmol/L, 0.3mmol/L, 0.4mmol/L or 0.5mmol/L, but not limited to the values listed, and other values not listed in the numerical range are also applicable;
in the third step, specifically, the mass concentration of the lithium ion conductor coating material in the mixed dispersion liquid is 200g/L, that is, 200g of the lithium ion conductor coating material should be added to 1L of the methanol solvent.
In the fourth step, the stirring time is 13h in concrete implementation;
in the fourth step, the rotation speed of stirring is 450r/min (stirring by the existing stirrer);
in the fourth step, specifically, the drying temperature is 180 ℃; the drying time is 8h;
in the fourth step, the mesh number of the screen used for sieving is 300 meshes in concrete implementation.
In the fourth step, concreteAt present, the surface in-situ modified all-solid-state battery high-nickel positive electrode material is a nickel-cobalt-aluminum positive electrode material, and the specific chemical formula is LiNi x Co y M z M' a O 2 X is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.2, a is more than or equal to 0 and less than or equal to 0.005, and x + y + z + a =1, and the component M is Mn or Al;
in the fourth step, the chemical formula of the surface in-situ modified all-solid-state battery high-nickel positive electrode material is LiNi x Co y M z M' a O 2 ；
Where 0.8. Ltoreq. X < 1, for example x can be 0.8, 0.9 or 0.95, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable;
where 0 < y < 0.2, for example y may be 0.05, 0.1 or 0.15, but is not limited to the values recited, and other values not recited within the numerical range are equally applicable.
Where 0 < z < 0.2, for example z can be 0.01, 0.03, 0.05, 0.1 or 0.15, but is not limited to the values listed, and other values not listed in the numerical range are equally suitable.
Where 0. Ltoreq. A.ltoreq.0.005, for example a may be 0, 0.001, 0.002, 0.003, 0.004 or 0.005, but is not limited to the values listed, and other values not listed in the numerical range are likewise suitable.
In addition, the invention provides a preparation method of the surface in-situ modified all-solid-state battery high-nickel positive electrode material, which is applied to the high-nickel positive electrode material of the lithium ion all-solid-state battery.
In addition, the invention also provides a lithium ion all-solid-state battery, which comprises the surface in-situ modified all-solid-state battery high-nickel positive electrode material prepared by the preparation method of the surface in-situ modified all-solid-state battery high-nickel positive electrode material.
In order to more clearly understand the technical solution of the present invention, the technical solution of the present invention is described below by specific examples.
Example 1.
Embodiment 1 of the invention provides a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material (namely, a nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiNbO in situ 3 ；
The surface of the nickel-cobalt-manganese anode material is coated with a polydopamine nano-layer in an in-situ polymerization manner.
In example 1, a method for preparing a surface in-situ modified all-solid-state battery high-nickel cathode material (i.e., a nickel-cobalt-manganese cathode material) includes the following steps:
firstly, taking ethanol as a ball milling agent, and ball milling and mixing Ni according to the formula amount at 300r/min 90 Co 2 Mn 8 (OH) 2 Precursor, zrO 2 2 And lithium hydroxide for 4 hours, drying, crushing and sieving to obtain a mixture, and then sintering the mixture for 12 hours at 740 ℃ in an oxygen atmosphere to obtain a sintered material;
in example 1, in the first step, 100g of a high nickel hydroxide precursor, 45g of LiOH (lithium hydroxide) as a lithium source, and ZrO as an additive were added 2 It was 0.4g.
Secondly, ball milling and mixing 1.2wt% of Nb serving as an ion conductor coating source 2 O 5 And sintering material obtained in the first step to obtain ball grinding material, and calcining the ball grinding material for 10 hours at 600 ℃ in air atmosphere to obtain LiNbO 3 Coating materials;
thirdly, dissolving dopamine hydrochloride and tris (hydroxymethyl) aminomethane together in 1L of methanol (the concentration of dopamine hydrochloride is 0.3mmol/L and the concentration of tris (hydroxymethyl) aminomethane is 0.3 mmol/L), and then dissolving 200g of the lithium ion conductor coating material (LiNbO) obtained in the second step 3 Coating material) is slowly added into the dopamine polymerization coating liquid to obtain mixed dispersion liquid;
in the third step, specifically, methanol is used as an analytical reagent and used as a solvent, tris (hydroxymethyl) aminomethane is dissolved in 1L of methanol to obtain a primary buffer solution with the preparation concentration of 0.3mmol/L, and dopamine hydrochloride is dissolved in the primary buffer solution with the preparation concentration of 0.3mmol/L, so that the dopamine polymerization coating solution is obtained.
And fourthly, stirring the mixed dispersion liquid at the room temperature for 13 hours at the rotating speed of 450r/min, introducing oxygen into the mixed dispersion liquid simultaneously to ensure that the lithium ion conductor coating material is polymerized to coat the polydopamine nano layer, filtering and separating, drying at the vacuum drying temperature of 180 ℃ for 8 hours, and then sieving by using a 300-mesh sieve to obtain the surface in-situ modified all-solid-state battery nickel-cobalt-manganese positive electrode material.
Example 2.
Embodiment 2 of the invention provides a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material (namely, a nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-aluminum cathode material is LiNi 0.92 Co 0.02 Mn 0.056 Sr 0.004 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiNbO in situ 3 ；
The surface of the nickel-cobalt-manganese cathode material is coated with a polydopamine nano-layer in an in-situ polymerization manner.
In example 2, a method for preparing a surface in-situ modified all-solid-state battery high-nickel cathode material (i.e., a nickel-cobalt-manganese cathode material) includes the following steps:
firstly, taking ethanol as a ball milling agent, and ball milling and mixing Ni according to the formula amount at 300r/min 92 Co 2 Mn 6 (OH) 2 Precursor, srCO 3 Mixing with lithium hydroxide for 4 hours, drying, crushing and sieving to obtain a mixture, and then sintering the mixture for 11 hours at 720 ℃ in an oxygen atmosphere to obtain a sintered material;
in example 2, in the first step, the high nickel hydroxide precursor was 100g, the lithium source, liOH (lithium hydroxide), was 46g, and the additive, srCO 3 It was 0.6g.
Secondly, ball milling and mixing 1.5wt% of ion conductor coated source Nb 2 O 5 And sintering material obtained in the first step to obtain ball grinding material, and calcining the ball grinding material for 10 hours at 600 ℃ in air atmosphere to obtain LiNbO 3 Coating materials;
thirdly, dopamine hydrochloride is addedDissolving in 1L methanol (dopamine hydrochloride concentration of 0.3mmol/L, and tris (hydroxymethyl) aminomethane concentration of 0.3 mmol/L), and coating with 200g of the lithium ion conductor (LiNbO) obtained in the second step 3 Coating material) is slowly added into the dopamine polymerization coating liquid to obtain mixed dispersion liquid;
in the third step, specifically, methanol is used as an analytical reagent and used as a solvent, tris (hydroxymethyl) aminomethane is dissolved in 1L of methanol to obtain a primary buffer solution with the preparation concentration of 0.3mmol/L, and dopamine hydrochloride is dissolved in the primary buffer solution with the preparation concentration of 0.3mmol/L, so that the dopamine polymerization coating solution is obtained.
And fourthly, stirring the mixed dispersion liquid at the room temperature for 13 hours at the rotating speed of 450r/min, introducing oxygen into the mixed dispersion liquid simultaneously to ensure that the surface of the lithium ion conductor coating material is polymerized in situ to coat the polydopamine nano layer, filtering and separating, drying at the vacuum drying temperature of 180 ℃ for 8 hours, and then sieving by using a 300-mesh sieve to obtain the surface in-situ modified all-solid-state battery nickel-cobalt-manganese positive electrode material.
Example 3.
The embodiment 3 of the invention provides a preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material (namely, a nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-aluminum cathode material is LiNi 0.88 Co 0.10 Al 0.016 Zr 0.004 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiNbO in situ 3 (ii) a The surface of the nickel-cobalt-aluminum cathode material is coated with the polydopamine nano-layer in an in-situ polymerization manner.
In example 3, a method for preparing a surface in-situ modified all-solid-state battery high-nickel cathode material (i.e., a nickel-cobalt-manganese cathode material) includes the following steps:
firstly, taking ethanol as a ball milling agent, and ball milling and mixing Ni according to the formula amount at 300r/min 88 Co 10 Mn 2 (OH) 2 Precursor, zrO 2 Mixing with lithium hydroxide for 4h, oven drying, pulverizing, and sieving to obtain mixtureThen sintering the mixture for 12 hours at 750 ℃ in an oxygen atmosphere to obtain a sintered material;
in example 3, in the first step, 100g of a high nickel hydroxide precursor, 46g of LiOH (lithium hydroxide) as a lithium source, and ZrO as an additive were added 2 It was 0.5g.
Secondly, ball milling and mixing 1wt% of ion conductor coated source Nb 2 O 5 And sintering the obtained sintered material to obtain a ball grinding material, and calcining the ball grinding material for 10 hours at 600 ℃ in an air atmosphere to obtain LiNbO 3 Coating materials;
thirdly, dissolving dopamine hydrochloride and tris (hydroxymethyl) aminomethane together in 1L of methanol (the concentration of dopamine hydrochloride is 0.3mmol/L, and the concentration of tris (hydroxymethyl) aminomethane is 0.3 mmol/L), and slowly adding 200g of the lithium ion conductor coating material obtained in the second step into the dopamine polymerization coating liquid to obtain a mixed dispersion liquid;
in the third step, specifically, methanol is used as an analytical reagent and used as a solvent, tris (hydroxymethyl) aminomethane is dissolved in 1L of methanol to obtain a primary buffer solution with the preparation concentration of 0.3mmol/L, and then dopamine hydrochloride is dissolved in the primary buffer solution with the preparation concentration of 0.3mmol/L, so that the dopamine polymerization coating solution is obtained.
And fourthly, stirring the mixed dispersion liquid at the room temperature for 13 hours at the rotating speed of 450r/min, introducing oxygen into the mixed dispersion liquid simultaneously to ensure that the lithium ion conductor coating material is polymerized to coat the polydopamine nano layer, filtering and separating, drying at the vacuum drying temperature of 180 ℃ for 8 hours, and then sieving by using a 300-mesh sieve to obtain the surface in-situ modified all-solid-state battery nickel-cobalt-aluminum cathode material.
Example 4.
Embodiment 5 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-aluminum cathode material is LiNi 0.8 Co 0.17 Al 0.025 Sr 0.005 O 2 ；
The surface of the nickel-cobalt-aluminum cathode material is coated with a fast ion conductor layer LiNbO in situ 3 ；
The surface of the nickel-cobalt-aluminum cathode material is coated with a polydopamine nano layer in an in-situ polymerization manner.
In example 4, a method for preparing a surface in-situ modified all-solid-state battery high-nickel cathode material (i.e., a nickel-cobalt-manganese cathode material) includes the following steps:
firstly, taking ethanol as a ball milling agent, and ball milling and mixing Ni according to the formula amount at 300r/min 80 Co 17 Al 3 (OH) 2 Precursor, srCO 3 Mixing with lithium hydroxide for 4 hours, drying, crushing and sieving to obtain a mixture, and then sintering the mixture for 14 hours at 780 ℃ in an oxygen atmosphere to obtain a sintered material;
in example 4, in the first step, the high nickel hydroxide precursor was 100g, the lithium source LiOH (lithium hydroxide) was 45g, and the additive SrCO 3 It was 0.8g.
Secondly, ball milling and mixing 0.8wt% of ion conductor coating source Nb 2 O 5 And sintering the obtained sintered material to obtain a ball grinding material, and calcining the ball grinding material for 10 hours at 600 ℃ in an air atmosphere to obtain LiNbO 3 Coating materials;
thirdly, dissolving dopamine hydrochloride and tris (hydroxymethyl) aminomethane together in 1L of methanol (the concentration of dopamine hydrochloride is 0.3mmol/L, and the concentration of tris (hydroxymethyl) aminomethane is 0.3 mmol/L), and then coating 200g of the lithium ion conductor (LiNbO) obtained in the second step 3 Coating material) is slowly added into the dopamine polymerization coating liquid to obtain mixed dispersion liquid;
in the third step, specifically, methanol is used as an analytical reagent and used as a solvent, tris (hydroxymethyl) aminomethane is dissolved in 1L of methanol to obtain a primary buffer solution with the preparation concentration of 0.3mmol/L, and dopamine hydrochloride is dissolved in the primary buffer solution with the preparation concentration of 0.3mmol/L, so that the dopamine polymerization coating solution is obtained.
And fourthly, stirring the mixed dispersion liquid at the room temperature for 13 hours at the rotating speed of 450r/min, introducing oxygen into the mixed dispersion liquid simultaneously to ensure that the lithium ion conductor coating material is polymerized to coat the polydopamine nano layer, filtering and separating, drying at the vacuum drying temperature of 180 ℃ for 8 hours, and then sieving by using a 300-mesh sieve to obtain the surface in-situ modified all-solid-state battery nickel-cobalt-aluminum cathode material.
Example 5.
Embodiment 5 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese cathode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiNbO in situ 3 ；
The surface of the nickel-cobalt-manganese anode material is coated with a polydopamine nano-layer in an in-situ polymerization manner.
In example 5, the preparation method of the nickel-cobalt-manganese cathode material is different from that of example 1 in that: the ion conductor cladding source Nb 2 O 5 The amount of (B) was 0.8wt% based on the amount of the sintering material, and the rest was the same as in example 1.
Example 6.
Embodiment 6 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer Li in situ 2 SiO 3 (ii) a The surface of the nickel-cobalt-manganese cathode material is coated with a polydopamine nano-layer in an in-situ polymerization manner.
In example 6, the preparation method of the nickel-cobalt-manganese cathode material is different from that of example 1 in that: the ion conductor coating source is SiO 2 The amount of addition was 0.9wt% of the sintered material, and the ball abrasive was calcined at 700 ℃ for 10 hours, the rest being the same as in example 1.
Example 7.
Embodiment 7 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiAlO in situ 2 ；
The surface of the nickel-cobalt-manganese cathode material is coated with a polydopamine nano layer in an in-situ polymerization manner.
In example 7, the preparation method of the nickel-cobalt-manganese positive electrode material is different from that of example 1 in that: the ion conductor coating source is Al 2 O 3 The amount of addition was 0.8wt% of the sintered material, and the ball grinding material was calcined at 750 ℃ for 10 hours, the remainder being the same as in example 1.
Example 8.
Embodiment 8 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer Li in situ 3 BO 3 ；
And simultaneously, the surface of the nickel-cobalt-manganese anode material is coated with the polydopamine nano layer in an in-situ polymerization manner.
In example 8, the preparation method of the nickel-cobalt-manganese positive electrode material is different from that of example 1 in that: the ion conductor coating source is H 3 BO 3 The amount of addition was 1.5wt% of the sintered material, and the ball mill was calcined at 280 ℃ for 8 hours, the rest being the same as in example 1.
Example 9.
Embodiment 9 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.92 Co 0.01 Mn 0.064 Sr 0.004 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiZrO in situ 2 ；
The surface of the nickel-cobalt-manganese cathode material is coated with a polydopamine nano layer in an in-situ polymerization manner.
In example 9, the preparation method of the nickel-cobalt-manganese positive electrode material is different from that of example 1 in that: the ion conductor coating source is ZrO 2 The amount of addition was 1.5wt% of the sintered material, and the ball mill was calcined at 600 ℃ for 9 hours, the rest being the same as in example 2.
Example 10.
Embodiment 10 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer Li in situ 4 Ti 5 O 12 ；
The surface of the nickel-cobalt-manganese anode material is coated with a polydopamine nano-layer in an in-situ polymerization manner.
In example 10, the preparation method of the nickel-cobalt-manganese positive electrode material is different from that of example 1 in that: the ion conductor coating source is TiO 2 The amount of addition was 0.8wt% of the sintered material, and the ball abrasive was calcined at 700 ℃ for 10 hours, the rest being the same as in example 1.
Example 11.
Embodiment 11 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiNbO in situ 3 ；
The surface of the nickel-cobalt-manganese anode material is coated with a polydopamine nano-layer in an in-situ polymerization manner.
In example 11, the preparation method of the nickel-cobalt-manganese positive electrode material is different from that of example 1 in that: the dopamine hydrochloride addition concentration is 0.1mmol/L, and the rest is the same as that of the example 1.
Example 12.
Embodiment 12 of the present invention provides a method for preparing a surface in-situ modified all-solid-state battery high-nickel positive electrode material (i.e., nickel-cobalt-manganese positive electrode material);
the chemical formula of the nickel-cobalt-manganese anode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
The surface of the nickel-cobalt-manganese anode material is coated with a fast ion conductor layer LiNbO in situ 3 ；
The surface of the nickel-cobalt-manganese cathode material is coated with a polydopamine nano layer in an in-situ polymerization manner.
In example 12, the preparation method of the nickel-cobalt-manganese positive electrode material is different from that of example 1 in that: the dopamine hydrochloride addition concentration is 0.5mmol/L, and the rest is the same as that of the example 1.
Comparative example 1.
The comparative example 1 provides a preparation method of a nickel-cobalt-manganese high-nickel positive electrode material, wherein the chemical formula of the nickel-cobalt-manganese high-nickel positive electrode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
In comparative example 1, the nickel-cobalt-manganese positive electrode material was prepared by the same method as in example 1 except that the nickel-cobalt-manganese high nickel positive electrode material was not coated with an ion conductor and was not coated with polydopamine, and the rest was the same as in example 1.
Comparative example 2
The comparative example 2 provides a preparation method of a nickel-cobalt-manganese high-nickel cathode material, wherein the chemical formula of the nickel-cobalt-manganese cathode material is LiNi 0.9 Co 0.02 Mn 0.077 Zr 0.003 O 2 ；
In comparative example 2, the nickel-cobalt-manganese positive electrode material was prepared by the same method as in example 1 except that the nickel-cobalt-manganese high-nickel positive electrode material was not coated with polydopamine, and the rest was the same as in example 1.
For the above examples and comparative examples, the high nickel positive electrode material provided in the above examples and comparative examples, acetylene black and polyvinylidene fluoride were mixed at a mass ratio of 94; and assembling a high-nickel positive pole piece, a lithium negative pole piece and sulfide electrolyte or halide electrolyte as solid electrolyte into the 2032 type button cell.
Through testing, the test methods and results of the high nickel cathode materials provided in the above examples and comparative examples are as follows:
the button cell assembled by the high-nickel cathode material provided by the above embodiment and the comparative example tests the specific capacity of the first discharge at 0.2C under the conditions of a charge and discharge current of 0.1C and a charge and discharge voltage of 2.5V-4.25V at 25 ℃. Meanwhile, the cycle retention rate of the material is tested for 50 times at 25 ℃ under 1C charging and discharging current. And performing an oxygen release temperature test: and (3) carrying out electrochemical performance test on the prepared battery at 25 ℃, wherein the test conditions are as follows: the voltage range is 3.0-4.3V, and a full electrode plate is taken for TG-MS test.
The test results are shown in table 1.
Table 1:
from table 1 above, the following aspects can be seen:
1. as is clear from examples 2 to 4 and example 1, the higher the nickel content of the positive electrode material, the higher the capacity thereof, but the lower the oxygen release temperature thereof, the worse the cycle performance thereof.
2. As is clear from examples 5 and 1, example 5 is presumed to reduce the amount of the ion conductor-coated source, resulting in a slight decrease in battery capacity and a decrease in cycle performance: the lithium ion conductor coating layer of the material prepared in example 5 may be unevenly coated.
3. Made of fruitExamples 6 to 10 and example 1 show that the lithium ion conductor coating layer LiNbO in example 1 3 In contrast, the lithium ion conductor clad layer Li 2 SiO 3 、LiZrO 2 And LiAlO 2 Will have a certain negative effect on the capacity of the anode material, and the lithium ion conductor coating layer Li 4 Ti 5 O 12 And Li 3 BO 3 There is a certain improvement in the capacity of the positive electrode material.
4. As can be seen from example 1 and comparative example 1, the nickel-cobalt-manganese high-nickel cathode material provided in comparative example 1 is not coated with a lithium ion conductor and polydopamine, and therefore, the battery performance thereof is compared with example 1: the phenomenon of obvious reduction can occur, and meanwhile, the oxygen release temperature is also reduced to a certain extent;
therefore, based on the technical scheme of the invention, the high-nickel cathode material subjected to surface in-situ modification can effectively reduce the side reaction with the solid electrolyte interface to avoid interface huge impedance, improve the lithium ion transmission efficiency, facilitate the transmission of lithium ions at the interface, achieve the effect of inhibiting oxygen release of the cathode material, and further improve the safety. Therefore, the performance of the all-solid-state lithium ion battery is remarkably improved.
5. As can be seen from example 1 and comparative example 2, the nickel-cobalt-manganese high-nickel cathode material provided in comparative example 2 is not coated with polydopamine, and although the battery performance is not much different from that of example 1, the oxygen release temperature is reduced. Thus illustrating that: the poly-dopamine nano layer can play a role in improving the safety of the battery.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention aims to solve the problem of mismatching of the interface of the anode and the electrolyte of the all-solid-state lithium ion battery and improve the performance of the high-nickel ternary anode material in the all-solid-state lithium ion battery.
2. In the in-situ coating process of the lithium ion conductor, the residual alkali on the surface of the material is fully utilized to reduce the gas generation of the battery, so that the electrical property of the anode material is improved. The coating layer can effectively reduce the side reaction with the solid electrolyte interface, avoid the huge impedance of the interface, improve the transmission efficiency of lithium ions and be beneficial to the transmission of the lithium ions at the interface. Therefore, the performance of the all-solid-state lithium ion battery can be remarkably improved. Meanwhile, the oxygen release safety problem of the anode material is improved by adopting the poly-dopamine nano-layer in-situ coating, and the poly-dopamine can absorb and fix the released oxygen free radicals, so that the effect of inhibiting the oxygen release of the anode material is achieved.
In summary, compared with the prior art, the preparation method and the application of the surface in-situ modified all-solid-state battery high-nickel positive electrode material and the lithium ion all-solid-state battery provided by the invention have scientific design, and the lithium ion conductor layer obtained by reacting residual alkali free lithium on the surface of the sintering material with the ion conductor coating source is utilized to prevent the damage of the surface structure of the positive electrode material and inhibit the mixed discharge of lithium and nickel, and the polydopamine nano-layer is adopted to improve the safety performance of the battery, so that the method has great practical significance.
The high-nickel anode material directly coats the lithium ion conductor layer and the polydopamine nano layer, changes the surface physical and chemical characteristics of the anode material, and reduces the damage to the surface structure of the anode material and further reduces the mixed discharge of lithium and nickel compared with the existing high-nickel anode material subjected to a water washing process.
According to the technical scheme, the ion conductor layer is coated in situ by fully utilizing the residual alkali on the surface of the material, so that the electrochemical performance of the anode material is improved by reducing the gas generation of the battery.
The high-nickel anode material provided by the invention has no problem of treatment of alkali-containing industrial wastewater, and is environment-friendly. The lithium ion conductor layer coated by the high-nickel anode material can improve the lithium ion transmission efficiency, and can avoid the occurrence of side reaction caused by the direct contact of the anode material and the solid electrolyte to cause huge interface impedance, thereby prolonging the service life of the all-solid-state battery;
in addition, the high-nickel anode material provided by the invention coats the poly-dopamine nano layer, and when the anode material releases oxygen during high-voltage charging and discharging, the poly-dopamine nano layer can fix released oxygen radicals, so that the safety of the all-solid-state battery is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a surface in-situ modified all-solid-state battery high-nickel positive electrode material is characterized by comprising the following steps:
the method comprises the following steps of firstly, uniformly mixing a high-nickel hydroxide precursor, a lithium source and an additive to obtain a mixture, and then sintering the mixture to obtain a sintered material;
step two, uniformly mixing an ion conductor coating source and the sintered material obtained in the step one, and then calcining to obtain a lithium ion conductor coating material with an ion conductor coating layer;
dissolving dopamine hydrochloride and tris (hydroxymethyl) aminomethane in methanol to obtain dopamine polymerization coating solution, and slowly adding the lithium ion conductor coating material obtained in the second step into the dopamine polymerization coating solution to obtain mixed dispersion solution;
and fourthly, stirring the mixed dispersion liquid at room temperature, introducing oxygen into the mixed dispersion liquid to enable the lithium ion conductor coating material to be polymerized and coated on the polydopamine nano layer, and filtering, separating, drying in vacuum and sieving to finally obtain the surface in-situ modified all-solid-state battery high-nickel positive electrode material.
2. The surface in-situ modified all-solid-state battery high-nickel cathode material and the preparation method thereof according to claim 1, wherein in the first step, the additive comprises any one or a combination of at least two of oxide, hydroxide, carbonate and nitrate of M';
wherein M' comprises any one or the combination of at least two of Zr, sr, nb, al, Y, W or Mg.
3. The surface in-situ modified all-solid-state battery high-nickel positive electrode material and the preparation method thereof as claimed in claim 1, characterized in that in the first step, the sintering temperature is 720-780 ℃, and the sintering time is 9-14 h;
in the first step, the sintering atmosphere is oxygen atmosphere;
in the first step, the mixing mode is specifically that first ball milling is carried out through a first ball milling mixer to realize mixing, so as to obtain ball grinding materials;
the rotating speed of the first ball milling is 300-400 r/min;
the time of the first ball milling is 2-4 h;
the ball milling agent used in the first ball milling comprises ethanol;
in the second step, the calcining temperature is 280-750 ℃ and the calcining time is 8-10 h;
in the second step, the atmosphere of the calcination is air atmosphere;
in the second step, the mixing mode is specifically that the second ball milling is carried out through a second ball milling mixer to realize mixing, so as to obtain ball grinding materials;
the rotating speed of the second ball milling is 100-300 r/min;
the time of the second ball milling is 1-3 h;
the ball milling agent used for the second ball milling comprises ethanol.
4. The surface in-situ modified all-solid-state battery high-nickel positive electrode material and the preparation method thereof according to claim 1, wherein in the first step, the lithium source includes at least one of lithium hydroxide and lithium carbonate.
5. The surface in-situ modified all-solid-state battery high-nickel cathode material and the preparation method thereof according to claim 1, characterized in that in the second step, an ion conductor layer is obtained by reacting residual alkali free lithium on the surface of the sintering material with an ion conductor coating source, wherein the addition amount of the ion conductor coating source accounts for 0.8-1.5% of the total mass of the sintering material;
the ion conductor cladding source comprises Nb 2 O 5 、SiO 2 、ZrO 2 、Al 2 O 3 、TiO 2 And H 3 BO 3 At least one of (a).
6. The surface in-situ modification all-solid-state battery high-nickel cathode material and the preparation method thereof as claimed in claim 1, wherein in the third step, the adding concentration of the tris (hydroxymethyl) aminomethane in the dopamine polymerization coating solution is 0.3-0.5 mmol/L;
in the third step, the adding concentration of the dopamine hydrochloride in the dopamine polymerization coating solution is 0.1-0.5 mmol/L;
in the mixed dispersion, the mass concentration of the lithium ion conductor coating material was 200g/L.
7. The surface in-situ modified all-solid-state battery high-nickel positive electrode material and the preparation method thereof as claimed in claim 1, wherein in the fourth step, the stirring time is 13h;
in the fourth step, the stirring speed is 450r/min;
in the fourth step, the drying temperature is 180 ℃; the drying time is 8h;
in the fourth step, the mesh number of the screen used for the sieving was 300 mesh.
8. The application of the preparation method of the surface in-situ modified all-solid-state battery high-nickel cathode material as claimed in any one of claims 1 to 7, which is characterized by being applied to the high-nickel cathode material of a lithium ion all-solid-state battery.
9. A lithium ion all-solid-state battery, which is characterized by comprising the surface in-situ modified all-solid-state battery high-nickel positive electrode material prepared by the preparation method of the surface in-situ modified all-solid-state battery high-nickel positive electrode material as claimed in any one of claims 1 to 7.
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| CN108232182A (en) * | 2016-12-13 | 2018-06-29 | 天津国安盟固利新材料科技股份有限公司 | A kind of modified nickel-cobalt lithium manganate cathode material and preparation method thereof |
| CN110890541A (en) * | 2019-11-21 | 2020-03-17 | 国联汽车动力电池研究院有限责任公司 | Preparation method of surface-modified lithium-rich manganese-based positive electrode material and lithium ion battery |
| CN113328069A (en) * | 2021-05-11 | 2021-08-31 | 电子科技大学 | Lithium phosphate coated high-nickel cathode material of lithium ion battery and preparation method of lithium phosphate coated high-nickel cathode material |
| CN114142008A (en) * | 2021-11-24 | 2022-03-04 | 蜂巢能源科技有限公司 | Cathode material for relieving oxygen release, preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108232182A (en) * | 2016-12-13 | 2018-06-29 | 天津国安盟固利新材料科技股份有限公司 | A kind of modified nickel-cobalt lithium manganate cathode material and preparation method thereof |
| CN110890541A (en) * | 2019-11-21 | 2020-03-17 | 国联汽车动力电池研究院有限责任公司 | Preparation method of surface-modified lithium-rich manganese-based positive electrode material and lithium ion battery |
| CN113328069A (en) * | 2021-05-11 | 2021-08-31 | 电子科技大学 | Lithium phosphate coated high-nickel cathode material of lithium ion battery and preparation method of lithium phosphate coated high-nickel cathode material |
| CN114142008A (en) * | 2021-11-24 | 2022-03-04 | 蜂巢能源科技有限公司 | Cathode material for relieving oxygen release, preparation method and application |
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