CN115241436A - 高首效锂掺杂硅氧化物复合负极材料及其制备方法 - Google Patents
高首效锂掺杂硅氧化物复合负极材料及其制备方法 Download PDFInfo
- Publication number
- CN115241436A CN115241436A CN202210943730.XA CN202210943730A CN115241436A CN 115241436 A CN115241436 A CN 115241436A CN 202210943730 A CN202210943730 A CN 202210943730A CN 115241436 A CN115241436 A CN 115241436A
- Authority
- CN
- China
- Prior art keywords
- lithium
- silicon oxide
- sio
- negative electrode
- doped silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 127
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 152
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 111
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 110
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 25
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 20
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 16
- 238000001228 spectrum Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 68
- 238000000576 coating method Methods 0.000 claims description 68
- 239000000843 powder Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000012071 phase Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000010405 anode material Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 24
- 238000012216 screening Methods 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 17
- 239000007790 solid phase Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000012792 core layer Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 239000007789 gas Substances 0.000 description 31
- 238000001816 cooling Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000007599 discharging Methods 0.000 description 20
- 230000001681 protective effect Effects 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 15
- 238000005229 chemical vapour deposition Methods 0.000 description 14
- 238000000151 deposition Methods 0.000 description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910004283 SiO 4 Inorganic materials 0.000 description 11
- 238000009830 intercalation Methods 0.000 description 11
- 230000002687 intercalation Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- -1 lithium silicates Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910018068 Li 2 O Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YJSAVIWBELEHDD-UHFFFAOYSA-N [Li].[Si]=O Chemical compound [Li].[Si]=O YJSAVIWBELEHDD-UHFFFAOYSA-N 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 5
- 229910000103 lithium hydride Inorganic materials 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 5
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052747 lanthanoid Inorganic materials 0.000 description 4
- 150000002602 lanthanoids Chemical class 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 239000012448 Lithium borohydride Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910001954 samarium oxide Inorganic materials 0.000 description 2
- 229940075630 samarium oxide Drugs 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 238000000408 29Si solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910008373 Li-Si-O Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910006757 Li—Si—O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- RXBBZJPEEIUBJG-UHFFFAOYSA-N [O].[Si].[Li] Chemical compound [O].[Si].[Li] RXBBZJPEEIUBJG-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62828—Non-oxide ceramics
- C04B35/62839—Carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62884—Coating the powders or the macroscopic reinforcing agents by gas phase techniques
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62894—Coating the powders or the macroscopic reinforcing agents with more than one coating layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/95—Products characterised by their size, e.g. microceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了高首效锂掺杂硅氧化物复合负极材料及其制备方法,涉及锂电负极材料技术领域,所述复合负极材料包括纳米硅、锂硅酸盐和导电碳层,所述复合负极材料的X射线衍射图谱中2θ为24.7±0.2°的Li2Si2O5(111)衍射峰强度为I1,X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰强度为I2,I1/I2<0.25;X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰面积为A1,X射线衍射图谱中2θ为28.4±0.3°的Si(111)衍射峰面积为A2,A2/A1≥1.0,本发明披露了通过材料各物相一定的构成比例能够使得材料达到高首效高比容量的效果。
Description
技术领域
本发明涉及锂电负极材料技术领域,具体涉及高首效锂掺杂硅氧化物复合负极材料及其制备方法。
背景技术
锂离子电池因具有工作电压高、循环使用寿命长、无记忆效应、自放电小、环境友好等优点,已被广泛应用于便携式电子产品和电动汽车中。目前,商业化的锂离子电池主要采用石墨类负极材料,但它的理论比容量仅为372mAh/g,无法满足未来锂离子电池对高能量密度的需求。现有的Si虽然理论容量高达4200mAh/g,但其膨胀达300%,使循环性能受到影响,导致市场推广和应用受到约束。与之相对应的硅氧材料,循环性能更好,但是首次效率低。在首次充电时,需要消耗20至50%的锂用于形成SEI膜和不可逆物质,这就大大降低了首次库伦效率。
提升硅氧化物材料首效行之有效的方式是预先对其进行锂掺杂,提前将硅氧化物材料中的不可逆耗锂相部分的反应掉。硅氧化物电化学嵌锂后可形成锂硅合金、锂硅酸盐和Li2O,其中锂硅酸盐种类非常多Li2O·nSiO2(n为模数),通常有Li2O·2SiO2(Li2Si2O5)、Li2O·SiO2(Li2SiO3)、Li2O·2/3SiO2(Li6Si2O7)和Li2O·1/2SiO2(Li4SiO4)。Yasuda等人根据Li-Si-O三元相图,从热力学角度分析SiO连续锂化时锂硅酸盐的物相演变为Li2Si2O5→Li2SiO3→Li4SiO4,即高模数向低模数转变(Thermodynamic analysis and effect ofcrystallinity for silicon monoxide negative electrode for lithium ionbatteries,J.Power Sources 2016,329,462-472),进一步嵌锂时,Li4SiO4分解成Li13Si4和Li2O;该文献公开了随着嵌锂深度增加,锂硅酸盐逐渐向高锂含量低模数的锂硅酸盐转化,说明Li2O和锂硅酸盐具有可逆性。文献Unraveling the Reaction Mechanisms of SiOAnodes for Li-Ion Batteries by Combining in Situ 7Li and ex Situ 7Li/29SiSolid-State NMR Spectroscopy.J.Am.Chem.Soc.2019,141(17),7014-7027研究了非晶SiO的锂化反应研究结果,公开了Li4SiO4在脱锂过程可转变成Li2SiO3,充放电过程是嵌锂产物(Li4SiO4和LixSi)和脱锂产物(Li4SiO4、Li2SiO3和SiOx)之间的物相可逆转换。文献Solid-State NMR and Electrochemical Dilatometry Study on Li+ Uptake/Extraction Mechanism in SiO Electrode.J.Electrochem.Soc.2007,154(12),A1112-A1117.和文献Nanosilicon electrodes for lithium-ion batteries:interfacialmechanisms studiedby hard and soft X-ray photoelectronspectroscopy.Chem.Mater.2012,24(6),1107-1115.公开报道了硅氧化物嵌锂过程形成的Li2O具有可逆性。因此,锂掺杂硅氧化物中初始锂硅酸盐的模数越低,嵌锂过程锂硅酸盐向终极物相转变消耗的锂就更少,有利于提高硅氧化物负极材料的首效。因此,锂掺杂硅氧化物材料中锂硅酸盐的物相和相对含量与其电化学性能密切相关。由于Li4SiO4的水溶性较高,锂掺杂硅氧一般都经过洗涤除杂过程,因而Li4SiO4难以存在于最终的锂掺杂硅氧化物材料中,通常残留的锂硅酸盐有Li2SiO3和Li2Si2O5。虽然现有技术中的预锂硅氧化物负极材料的首效有了一定程度的提升,但在0.8V截止电位的首效仍然较低,例如≤83.5%,且始终无法突破,而目前高镍正极材料的首次效率可达90%,未来进一步提供电芯能量密度,预锂硅氧化物负极材料的0.8V首效还需进一步提升。
发明内容
为解决上述问题,本发明提供了新的高首效含锂硅氧化物复合负极材料,所述复合负极材料具有特定的物相构成比例,具有高首效和高比容量,并提供了相应的制备方法。具体方案如下:
在本发明的各种实施方案中,提供了高首效锂掺杂硅氧化物复合负极材料,包括纳米硅、锂硅酸盐和导电碳层,所述复合负极材料的X射线衍射图谱中2θ为24.7±0.2°的Li2Si2O5(111)衍射峰强度为I1,X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰强度为I2,I1/I2<0.25,作为示例,例如,I1/I2<0.24,I1/I2<0.23,I1/I2<0.22,I1/I2<0.21,I1/I2<0.20,I1/I2<0.19,I1/I2<0.18,I1/I2<0.17,I1/I2<0.16,I1/I2<0.15,I1/I2<0.14,I1/I2<0.13,I1/I2<0.12,I1/I2<0.10,I1/I2<0.09,I1/I2<0.08,I1/I2<0.07,I1/I2<0.06,I1/I2<0.05,I1/I2<0.04,I1/I2<0.03,I1/I2<0.02,或I1/I2<0.01。
在某些实施方案中,所述高首效锂掺杂硅氧化物复合负极材料的X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰面积为A1,X射线衍射图谱中2θ为28.4±0.3°的Si(111)衍射峰面积为A2,A2/A1≥1.0,作为示例,例如A2/A1≥1.1,A2/A1≥1.2,A2/A1≥1.3,A2/A1≥1.4,A2/A1≥1.5,A2/A1≥1.6,A2/A1≥1.7,A2/A1≥1.8,A2/A1≥1.9,A2/A1≥2.0,A2/A1≥2.1,A2/A1≥2.2,A2/A1≥2.3,A2/A1≥2.4,A2/A1≥2.5,A2/A1≥2.6,A2/A1≥2.7,A2/A1≥2.8,A2/A1≥2.9,或A2/A1≥3.0。
在某些实施方案中,所述锂掺杂硅氧化物复合负极材料为核壳结构;所述核壳结构包括核层和壳层;所述核层包括纳米硅和锂硅酸盐,所述锂硅酸盐含有Li2SiO3和Li2Si2O5的一种或两种,所述壳层包括均匀分布于核层表面的导电碳层,任选地还包括耐水涂层。
在某些实施方案中,以含锂硅氧化物复合负极材料的总质量为100wt%计,其中碳材料的质量百分比为0.5至10wt%,例如0.6至10wt%,0.7至9wt%,0.8至8wt%,例如0.5wt%、0.6wt%、0.7wt%、0.8wt%、0.9wt%、1wt%、2wt%、2.5wt%、5wt/%、6wt%、7wt%、8wt%、9wt%或10wt%等,进一步优选为2至6wt%;所述碳材料包括硅氧化物SiOx中的包覆碳以及耐水涂层中的包覆碳,其中耐水涂层的包覆碳含量为复合负极材料的0.5-4wt%,例如0.5wt%、0.6wt%、0.7wt%、0.8wt%、0.9wt%、1wt%、2wt%、2.5wt%、3wt%、3.5wt%、4wt%。
在某些实施方案中,所述纳米硅为单质硅,纳米硅的平均晶粒尺寸为3至20nm,在某些实施方案中,纳米硅的平均晶粒尺寸为3至10nm,在某些实施方案中,纳米硅的平均晶粒尺寸为4至8nm。
在某些实施方案中,所述高首效锂掺杂硅氧化物复合负极材料的D50为2至15μm,D90为5至25μm。
如本文中所使用的术语“D50”,旨在表示某一个样品的累计粒度分布百分数达到50%时所对应的粒径。它的物理意义是粒径大于它的颗粒占50%,小于它的颗粒也占50%,D50也叫中位径或中值粒径。D代表粉体颗粒的直径,D50表示累计50%点的直径(或称50%通过粒径)。
如本文中所使用的术语“D90”,旨在表示某一个样品的累计粒度分布数达到90%时所对应的粒径。它的物理意义是粒径小于(或大于)它的颗粒占90%。
本发明还提供上述高首效锂掺杂硅氧化物复合负极材料的制备方法,包括以下步骤:
S1、将硅氧化物SiOx、锂源和Li2SiO3成核添加剂采用固相混合方式进行混合,形成预锂前驱体;
S2、将预锂前驱体在真空或非氧化气氛下热处理,然后解聚、筛分,得到复合物粉体;
S3、对步骤S2形成的复合物粉体进行除杂改性处理,得到锂掺杂硅氧化物复合负极材料。
在某些优选实施方案中,本发明还提供上述高首效锂掺杂硅氧化物复合负极材料的制备方法,包括以下步骤:
S1、将硅氧化物SiOx、锂源和Li2SiO3成核添加剂采用固相混合方式进行混合,形成预锂前驱体;
S2、将预锂前驱体在真空或非氧化气氛下热处理,然后解聚、筛分,得到复合物粉体;
S3、对步骤S2形成的复合物粉体进行除杂改性处理,得到锂掺杂硅氧化物复合负极材料中间体;作为宽泛的理解,所述锂掺杂硅氧化物复合负极材料中间体也可以是锂掺杂硅氧化物复合负极材料的形式之一;
S4、对步骤S3形成的锂掺杂硅氧化物复合负极材料中间体进行表面耐水涂层修饰得到锂掺杂硅氧化物复合负极材料。
进一步地,各物质质量份数为:硅氧化物SiOx100份、锂源5至20份、Li2SiO3成核添加剂0.02至1份。
进一步地,所述硅氧化物SiOx中,0.7≤x≤1.3。
进一步地,所述硅氧化物SiOx可以碳包覆也可以不经过碳包覆。可选地,所述硅氧化物SiOx经过碳包覆,作为示例,碳包覆方式为气相包覆或固相包覆中的任意一种,硅氧化物SiOx中碳包覆的质量百分数为0至6%,例如0.1至6%,例如0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、2wt%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%。
进一步地,所述气相包覆的有机碳源气体包括甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的一种、两种或两种以上。
进一步地,气相包覆包括以下步骤:将硅氧化物SiOx置于回转炉中,通入保护性气氛,升温至600至1000℃,通入有机碳源气体,保温0.5至8h后冷却,得到碳包覆硅氧化物。
进一步地,所述固相包覆的碳源为沥青、聚乙烯粉、糖类和有机酸的一种、两种或两种以上混合物。
进一步地,固相碳包覆包括以下步骤:将硅氧化物SiOx与碳源混合置于混合机种进行混合,混合时间0.5至4h,混合机转速300至1500rpm,得到含碳源的混合物,然后将含碳混合物置于碳化炉中进行炭化,炭化温度为600至1000℃,炭化时间2至8h冷却出料,得到碳包覆硅氧化物材料。
进一步地,所述锂源包括氢化锂、烷基锂、金属锂、氢化铝锂、氨基锂、氮化锂、碳化锂、硅化锂或硼氢化锂中的一种、两种或两种以上混合锂源。
进一步地,所述Li2SiO3成核添加剂包括或者为稀土金属氧化物。在本发明中,成核添加剂可以降低Li2SiO3的形核能垒,同时也能够加速Li2Si2O5向Li2SiO3的转变,使得相同制备工艺条件下,添加了Li2SiO3成核添加剂后,烧成后制备的锂掺杂硅氧化物复合负极中Li2SiO3量多,Li2Si2O5量少。
进一步地,所述稀土金属氧化物为元素周期表中原子序数为57到71的15种镧系元素氧化物,以及与镧系元素化学性质相似的钪和钇共17种元素的氧化物,进一步优选为氧化镧、氧化铈、氧化镨、氧化钕、氧化钐和氧化钇中的至少一种。
进一步地,所述混合时间为0.5至10h,刀具间隙宽度为0.01至0.5cm,混合机转速为800至2500rpm。
进一步地,所述热处理温度为550至900℃,处理时间为2至8h,更进一步地,所述热处理温度为600至800℃,例如600℃、650℃、700℃、750℃,或800℃,等等,可选地,处理时间为2至5h,例如,2h,3h,4h,或5h。
进一步地,所述热处理在非氧化气氛下进行,进一步优选为惰性气体气氛,所述惰性气体包括氦气、氩气中的至少一种。
进一步地,所得材料的D50为2至15μm,D90为5至25μm,进一步地,D50为3至10μm,D90为9至15μm。
进一步地,所述步骤S3的除杂改性处理为洗涤,将步骤S2制备的复合物粉体置于溶液A中进行浸渍处理,浸渍使活性锂从含锂硅化物颗粒表面脱离;所述溶液A包括醇、弱碱、弱酸、水中的一种,或水与醇、弱碱、弱酸中至少一种的混合物。
进一步地,复合物粉体浸渍于溶液A之后,进行固液分离,固液分离可以采用离心、抽滤或者压滤的方式进行。
进一步地,对固液分离后的固体进行干燥处理。干燥气氛为空气、真空或者非氧化性气氛。干燥温度为40至150℃,进一步优选为40至100℃。干燥时间为6至48h,进一步优选为6至24h。
进一步地,所述步骤S4的耐水涂层可以是疏水聚合物,也可以是隔水无机物,进一步优选为碳涂层;所述碳涂层采用气相包覆或固相包覆中的任意一种包覆在核层表面;耐水涂层包覆占复合负极材料的质量百分数为0.5至4%;进一步优选为气相包覆。
进一步地,当耐水涂层为气相包覆的碳涂层时,气相包覆的有机碳源气体包括甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的一种、两种或两种以上;气相包覆包括以下步骤:将锂掺杂硅氧化物复合负极材料中间体放入CVD回转炉中,通入保护气体,升温至600至1000℃,通入有机碳源气体,保温0.5至8h,冷却出料,解聚,筛分,得到有耐水涂层包覆的高首效锂掺杂硅氧化物复合负极材料;所述保护气体优选氮气。
有益效果
本发明的有益效果在于:本发明不将研发角度放在掺杂元素优化或极片制备工艺优化来避免材料缺陷方面,或者寻求新的材料物相以提升材料性能,而是直接着眼于材料的各物相构成比例,提供了一种区别于以往的含锂硅氧复合负极材料的构成,即Li2Si2O5(111)衍射峰强度I1比Li2SiO3(111)衍射峰强度I2,I1/I2<0.25,Li2Si2O5(111)衍射峰面积A2比Li2SiO3(111)衍射峰面积A1,A2/A1≥1.0。硅氧化物负极材料在嵌锂过程中形成锂硅酸盐,随着嵌锂量的增加,形成的锂硅酸盐物相依次为Li2Si2O5、Li2SiO3和Li4SiO4,也就是说初始形成的Li2Si2O5可以继续嵌锂形成Li2SiO3物相,同时Li2SiO3还可以继续嵌锂形成Li4SiO4物相,因此,锂掺杂硅氧负极材料中的锂硅酸盐物相种类和相对含量与该负极材料的首次库伦效率密切相关。由于锂掺杂硅氧化物负极材料需要经过水洗除杂工序,且Li4SiO4物相的水溶性非常好,很容易被彻底清除,所以锂掺杂硅氧化物负极材料中Li2Si2O5和Li2SiO3的相对含量与该负极材料的首次库伦效率强相关。根据硅氧化物负极的嵌锂反应原理,锂掺杂硅氧化物负极材料中锂硅酸盐物相有Li2Si2O5和Li2SiO3,其中Li2SiO3的相对含量越多,复合负极材料的首次库伦效率就越高。因此,具有本发明所述特征的含锂硅氧复合负极材料,嵌锂过程不可逆锂消耗非常少,该负极材料具备高首效和高比容量的特点,0.8V首效可达84%以上,可逆比容量可达1300mAh/g以上。本发明提供的制备方法简单,环境友好无污染,适用于进行产业化大规模化生产。
附图说明
图1是本发明实施例1-2制备的材料X衍射图;
图2是本发明实施例2-3制备的材料X衍射图;
图3是本发明实施例2-3制备的材料扫描电镜图;
图4是本发明实施例2-3制备的材料首次充放电曲线。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。
为更好地理解本发明,下面结合实施例对本发明作进一步说明,但是本发明的实施方式不限于此。
第一方面,本发明提供高首效锂掺杂硅氧化物复合负极材料,包括纳米硅、锂硅酸盐、导电碳层,任选地,进一步还可以包括表面耐水涂层,所述复合负极材料X射线衍射图谱中2θ为24.7±0.2°的Li2Si2O5(111)衍射峰强度为I1,X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰强度为I2,I1/I2<0.25。
进一步地,所述高首效锂掺杂硅氧化物复合负极材料,复合负极材料X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰面积为A1,X射线衍射图谱中2θ为28.4±0.3°的Si(111)衍射峰面积为A2,A2/A1≥1.0。
作为本发明的优选技术方案,所述锂掺杂硅氧化物复合负极材料为核壳结构;所述核壳结构包括核层和壳层;所述核层包括纳米硅和锂硅酸盐,所述锂硅酸盐含有Li2SiO3和Li2Si2O5的一种或两种,所述壳层为均匀分布于核层表面的导电碳层和/或耐水涂层。
在示例性实施方案中,所述复合负极材料的X射线衍射图谱中2θ为24.7±0.2°的Li2Si2O5(111)衍射峰强度为I1,X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰强度为I2,I1/I2<0.25。
进一步地,所述纳米硅为单质硅,纳米硅的平均晶粒尺寸3至20nm,优选为3至10nm,进一步优选为4至8nm。
进一步地,以含锂硅氧化物复合负极材料的总质量为100wt%计,其中碳材料的质量百分比为0.5至10wt%,如0.5wt%、1wt%、2wt%、2.5wt%、5wt/%、6wt%、7wt%、8wt%、9wt%或10wt%等,进一步优选为2至6wt%。进一步地,所述高首效锂掺杂硅氧化物复合负极材料,D50为2至15μm,D90为5至25μm。
第二方面,本发明提供上述高首效锂掺杂硅氧化物复合负极材料的制备方法,但不作为对本发明技术方案的限制,制备方法包括以下步骤:
S1、将硅氧化物SiOx、锂源和Li2SiO3成核添加剂采用固相混合方式进行混合,形成均匀的预锂前驱体;
S2、将预锂前驱体在真空或非氧化气氛下热处理,然后解聚、筛分,得到复合物粉体;
S3、对步骤S2形成的复合物粉体进行除杂改性处理,得到锂掺杂硅氧化物复合负极材料中间体;
S4、对步骤S3形成的锂掺杂硅氧化物复合负极材料中间体进行表面耐水涂层修饰得到锂掺杂硅氧化物复合负极材料。
进一步地,S1步骤中各物质质量份数为:硅氧化物100份、锂源5至20份、Li2SiO3成核添加剂0.02至1份。
进一步地,所述硅氧化物SiOx中,0.7≤x≤1.3。
进一步地,所述硅氧化物SiOx可以是碳包覆的也可以不经过碳包覆,碳包覆方式为气相包覆或固相包覆中的任意一种,硅氧化物SiOx中碳包覆的质量百分数为0至6%。
进一步地,所述气相包覆的有机碳源气体包括甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的一种、两种或两种以上。
进一步地,气相包覆包括以下步骤:将硅氧化物置于回转炉中,通入保护性气氛,升温至600至1000℃,通入有机碳源气体,保温0.5至8h后冷却,得到碳包覆硅氧化物。
进一步地,所述固相包覆的碳源为沥青、聚乙烯粉、糖类和有机酸的一种、两种或两种以上混合物。
进一步地,固相碳包覆包括以下步骤:将硅氧化物与碳源混合置于混合机种进行混合,混合时间0.5至4h,混合机转速300至1500rpm,得到含碳源的混合物,然后将含碳混合物置于碳化炉中进行炭化,炭化温度为600至1000℃,炭化时间2至8h冷却出料,得到碳包覆硅氧化物材料。
进一步地,所述锂源包括氢化锂、烷基锂、金属锂、氢化铝锂、氨基锂、氮化锂、碳化锂、硅化锂或硼氢化锂中的一种、两种或两种以上混合锂源。
进一步地,所述Li2SiO3成核添加剂为一种或任意两种或两种以上稀土金属氧化物的混合物。
进一步地,所述稀土金属氧化物为元素周期表中原子序数为57到71的15种镧系元素氧化物,以及与镧系元素化学性质相似的钪和钇共17种元素的氧化物,进一步优选为氧化镧、氧化铈、氧化镨、氧化钕、氧化钐和氧化钇中的至少一种。
进一步地,所述混合时间为0.5至10h,刀具间隙宽度为0.01至0.5cm,混合机转速为800至2500rpm。
进一步地,所述步骤S2的热处理温度为550至900℃,例如,550℃、600℃、650℃、700℃、750℃、800℃、850℃或900℃,处理时间为2至8h,进一步优选为热处理温度为600至800℃,处理时间为2至5h。
进一步地,所述热处理,在非氧化气氛下进行,进一步优选为惰性气体气氛,所述惰性气体包括氦气、氩气中的至少一种。
进一步地,所得粉体材料的D50为2至15μm,D90为5至25μm,进一步优选为D50为3至10μm,D90为9至15μm。
进一步地,所述步骤S3的除杂改性处理为洗涤,将步骤S2制备的复合物粉体置于溶液A中进行浸渍处理,浸渍使活性锂从含锂硅化物颗粒表面脱离;所述溶液A包括醇、弱碱、弱酸、水中的一种,或水与醇、弱碱、弱酸中至少一种的混合物。
进一步地,复合物粉体浸渍于溶液A之后,进行固液分离,固液分离可以采用离心、抽滤或者压滤的方式进行。
进一步地,对固液分离后的固体进行干燥处理。干燥气氛为空气、真空或者非氧化性气氛。干燥温度为40至150℃,进一步优选为40至100℃。干燥时间为6至48h,进一步优选为6至24h。
进一步地,所述步骤S4的耐水涂层可以是疏水聚合物,也可以是隔水无机物,进一步优选为碳涂层;所述碳涂层采用气相包覆或固相包覆中的任意一种包覆在核层表面;耐水涂层包覆占复合负极材料的质量百分数为0.5至4%;进一步优选为气相包覆。
进一步地,当耐水涂层为气相包覆的碳涂层时,气相包覆的有机碳源气体包括甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的一种、两种或两种以上;气相包覆包括以下步骤:将锂掺杂硅氧化物复合负极材料中间体放入CVD回转炉中,通入保护气体,升温至600至1000℃,通入有机碳源气体,保温0.5至8h,冷却出料,解聚,筛分,得到有耐水涂层包覆的高首效锂掺杂硅氧化物复合负极材料;所述保护气体优选氮气。
第三方面,本发明提供了一种锂离子电池,锂离子电池包含所述第一方面的高首效锂掺杂硅氧化物复合负极材料。
对比例1锂掺杂硅氧化物复合负极材料(A2/A1≥1.0,I1/I2>0.25)
S1、称量D50为4.8μm,D90为8.0μm的未经碳包覆的硅氧化物粉体SiO0.7质量分数100份与氨基锂质量分数20份进行VC混合,混合转速600rpm,混合时间2h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行550℃高温热处理,热处理保温时间4h,热处理气氛为Ar气,降温后解聚筛分得到复合粉体;
S3、对步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料质量比为3:1,洗涤搅拌速度300rpm,搅拌时间2h,随后采用抽滤的方式进行固液分离,得到具有一定含湿率的泥状物料,然后将含湿物料放入真空干燥箱中进行干燥,干燥温度80℃,干燥时间12h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,800℃沉积0.5h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为0.5%。
对比例2锂掺杂硅氧化物复合负极材料(A2/A1≥1.0,I1/I2>0.25)
原材料制备:对D50为2.5μm,D90为5.0μm的硅氧化物粉体SiO0.89进行化学气相沉积碳包覆,SiO0.89粉体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,850℃沉积3.0h,冷却出料得到碳包覆的硅氧化物材料,碳包覆量为4%。
S1、称量上述方法制备的碳包覆硅氧化材料质量分数100份与氢化锂质量分数12.5份进行VC混合,混合转速400rpm,混合时间3h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行680℃高温热处理,热处理保温时间8h,热处理气氛为N2气,降温后解聚筛分得到复合粉体;
S3、对上述步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料比为6:1,洗涤搅拌速度500rpm,搅拌时间2h,随后采用压滤的方式进行固液分离,压滤后使用无水乙醇进行润洗3遍,得到具有一定含湿率的泥状物料,然后将含湿物料放入鼓风干燥箱中进行干燥,干燥温度80℃,干燥时间16h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙烯作为碳源,通入氮气作为保护性气氛,850℃沉积1h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为6%。
对比例3锂掺杂硅氧化物复合负极材料(A2/A1≥1.0,I1/I2>0.25)
原材料制备:对D50为10.0μm,D90为25.0μm的硅氧化物粉体SiO0.95进行化学气相沉积碳包覆,SiO0.95粉体放入CVD回转炉中,通入甲烷作为碳源,通入氮气作为保护性气氛,1000℃沉积2.0h,冷却出料得到碳包覆的硅氧化物材料,碳包覆量为3%。
S1、称量上述方法制备的碳包覆硅氧化材料质量分数100份与氮化锂质量分数5份进行VC混合,混合转速400rpm,混合时间3h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行900℃高温热处理,热处理保温时间3h,热处理气氛为Ar气,降温后解聚筛分得到复合粉体;
S3、对上述步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料比为3:1,洗涤搅拌速度500rpm,搅拌时间2h,随后采用压滤的方式进行固液分离,压滤后使用无水乙醇进行润洗3遍,得到具有一定含湿率的泥状物料,然后将含湿物料放入鼓风干燥箱中进行干燥,干燥温度80℃,干燥时间16h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,800℃沉积1h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为4.5%。
对比例4锂掺杂硅氧化物复合负极材料(A2/A1≥1.0,I1/I2>0.25)
原材料制备:对D50为6.0μm,D90为10.0μm的硅氧化物粉体SiO1.3进行固相碳包覆,SiO1.3粉体与碳源沥青按质量百分比100:10进行称量,然后进行VC混合,混合转速500rpm,混合时间3h,混合均匀后将物料放入辊道窑中进行碳化处理,碳化温度900℃,碳化高温保温时间5h,冷却出料得到碳包覆的硅氧化物材料,碳包覆量为6%。
S1、称量上述方法制备的碳包覆硅氧化材料质量分数100份与烷基锂质量分数10.8份进行VC混合,混合转速600rpm,混合时间2h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行800℃高温热处理,热处理保温时间5h,热处理气氛为N2气,降温后解聚筛分得到复合粉体;
S3、对上述步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料比为6:1,洗涤搅拌速度500rpm,搅拌时间2h,随后采用压滤的方式进行固液分离,得到具有一定含湿率的泥状物料,然后将含湿物料放入鼓风干燥箱中进行干燥,干燥温度80℃,干燥时间16h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙烯作为碳源,通入氮气作为保护性气氛,850℃沉积2h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为10%。
本对比例1至4所制备的锂掺杂硅氧化物复合负极材料的工艺具体参数见表1。
表1对比例1至4工艺具体参数
本对比例1至4所制备的锂掺杂硅氧化物复合负极材料的配料参数见表2。
表2对比例1至4配料参数
硅氧化物份数 | 锂源份数 | |
对比例1 | 100 | 20.0 |
对比例2 | 100 | 12.5 |
对比例3 | 100 | 5.0 |
对比例4 | 100 | 10.8 |
以下实施例采用和对应的对比例相同的处理步骤和参数,不同之处在于实施例相比于参考对比例仅在混合时额外添加了Li2SiO3成核添加剂,其中成核添加剂的添加方式和添加量见表3。
表3实施例1至4成核添加剂的添加方式和添加量
参考对比例 | Li<sub>2</sub>SiO<sub>3</sub>成核添加剂种类和用量 | |
实施例1-1 | 对比例1 | 0.15wt%氧化镧 |
实施例1-2 | 对比例1 | 1.0wt%氧化镨 |
实施例1-3 | 对比例1 | 0.02wt%氧化钕 |
实施例2-1 | 对比例2 | 0.15wt%氧化钕和0.15wt%氧化镧 |
实施例2-2 | 对比例2 | 0.22wt%氧化铈 |
实施例2-3 | 对比例2 | 0.10wt%氧化钇、0.10wt%氧化钕和0.20wt%氧化镧 |
实施例3-1 | 对比例3 | 0.20wt%氧化钇 |
实施例3-2 | 对比例3 | 0.10wt%氧化镨 |
实施例3-3 | 对比例3 | 0.20wt%氧化钕 |
实施例4-1 | 对比例4 | 0.10wt%氧化铈和0.25wt%氧化钪 |
实施例4-2 | 对比例4 | 0.35wt%氧化钪 |
实施例4-3 | 对比例4 | 0.30wt%氧化镨和0.35wt%氧化钕 |
对比例5锂掺杂硅氧化物复合负极材料(A2/A1<1.0,I1/I2≥0.25)
原材料制备:对D50为2.5μm,D90为5.0μm的硅氧化物粉体SiO1.1进行化学气相沉积碳包覆,SiO1.1粉体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,850℃沉积3.0h,冷却出料得到碳包覆的硅氧化物材料,碳包覆量为4%。
S1、称量上述方法制备的碳包覆硅氧化材料质量分数100份与氢化锂质量分数12份进行VC混合,混合转速400rpm,混合时间3h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行500℃高温热处理,热处理保温时间8h,热处理气氛为N2气,降温后解聚筛分得到复合粉体;
S3、对上述步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料比为6:1,洗涤搅拌速度500rpm,搅拌时间2h,随后采用压滤的方式进行固液分离,压滤后使用无水乙醇进行润洗3遍,得到具有一定含湿率的泥状物料,然后将含湿物料放入鼓风干燥箱中进行干燥,干燥温度80℃,干燥时间16h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,700℃沉积0.5h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为4.5%。
对比例6锂掺杂硅氧化物复合负极材料(A2/A1<1.0,I1/I2≥0.25)
原材料制备:对D50为2.5μm,D90为5.0μm的硅氧化物粉体SiO1.0进行化学气相沉积碳包覆,SiO1.0粉体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,850℃沉积1.5h,冷却出料得到碳包覆的硅氧化物材料,碳包覆量为3%。
S1、称量上述方法制备的碳包覆硅氧化材料质量分数100份与氨基锂质量分数10份进行VC混合,混合转速400rpm,混合时间3h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行420℃高温热处理,热处理保温时间16h,热处理气氛为N2气,降温后解聚筛分得到复合粉体;
S3、对上述步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料比为6:1,洗涤搅拌速度500rpm,搅拌时间2h,随后采用压滤的方式进行固液分离,压滤后使用无水乙醇进行润洗3遍,得到具有一定含湿率的泥状物料,然后将含湿物料放入鼓风干燥箱中进行干燥,干燥温度80℃,干燥时间16h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,650℃沉积1h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为3.5%。
对比例7锂掺杂硅氧化物复合负极材料(A2/A1<1.0,I1/I2<0.25)
原材料制备:对D50为2.5μm,D90为5.0μm的硅氧化物粉体SiO1.1进行化学气相沉积碳包覆,SiO1.1粉体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,850℃沉积3.0h,冷却出料得到碳包覆的硅氧化物材料,碳包覆量为4%。
S1、称量上述方法制备的碳包覆硅氧化材料质量分数100份与氢化锂质量分数12份,并加入氧化钇、氧化钕和氧化镧,三者加入的质量分别占物料总质量的质量百分数为:0.10%、0.10%和0.20%,进行VC混合,混合转速400rpm,混合时间3h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行500℃高温热处理,热处理保温时间8h,热处理气氛为N2气,降温后解聚筛分得到复合粉体;
S3、对上述步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料比为6:1,洗涤搅拌速度500rpm,搅拌时间2h,随后采用压滤的方式进行固液分离,压滤后使用无水乙醇进行润洗3遍,得到具有一定含湿率的泥状物料,然后将含湿物料放入鼓风干燥箱中进行干燥,干燥温度80℃,干燥时间16h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,700℃沉积0.5h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为4.5%。
对比例8锂掺杂硅氧化物复合负极材料(A2/A1<1.0,I1/I2<0.25)
原材料制备:对D50为2.5μm,D90为5.0μm的硅氧化物粉体SiO1.0进行化学气相沉积碳包覆,SiO1.0粉体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,850℃沉积1.5h,冷却出料得到碳包覆的硅氧化物材料,碳包覆量为3%。
S1、称量上述方法制备的碳包覆硅氧化材料质量分数100份与氨基锂质量分数10份,并加入氧化钇、氧化钕和氧化镧,三者加入的质量分别占物料总质量的质量百分数为:0.10%、0.30%和0.30%,进行VC混合,混合转速400rpm,混合时间3h,混合后得到预锂前驱体;
S2、将预锂前驱体在箱式炉中进行420℃高温热处理,热处理保温时间16h,热处理气氛为N2气,降温后解聚筛分得到复合粉体;
S3、对上述步骤2制备的复合粉体进行洗涤处理,洗涤溶剂为去离子水,水料比为6:1,洗涤搅拌速度500rpm,搅拌时间2h,随后采用压滤的方式进行固液分离,压滤后使用无水乙醇进行润洗3遍,得到具有一定含湿率的泥状物料,然后将含湿物料放入鼓风干燥箱中进行干燥,干燥温度80℃,干燥时间16h,得到锂掺杂硅氧化物复合负极材料中间体;
S4、将上述步骤3制备的中间体进行化学气相沉积碳包覆,中间体放入CVD回转炉中,通入乙炔作为碳源,通入氮气作为保护性气氛,650℃沉积1h,冷却出料,解聚,筛分400目,得到锂掺杂硅氧化物复合负极材料,复合负极材料碳含量为3.5%。
产品检测:
测试方法包括:
1、晶体结构表征:将实施例和对比例制备的锂掺杂硅氧化物复合负极材料进行晶体结构表征。XRD测试采用荷兰PANalytical帕纳科粉末衍射仪Xpert3Powder,测试电压40KV,测试电流40mA,扫描范围10至90°,扫描步长0.008°,每步扫描时间12s。
所述材料的Si平均晶粒尺寸的表征方法为使用X射线衍射仪,对2至theta范围内的10至90°进行扫描,然后对2θ范围内的26至30°进行拟合得到Si(111)峰的半峰宽,使用谢乐公式计算得到Si晶粒的平均尺寸。
所述X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰面积A1,所述X射线衍射图谱中2θ为28.4±0.3°的Si(111)衍射峰面积A2,计算A2/A1比值。
所述峰面积计算采用Jade 5.0对XRD结果进行拟合步骤如下:
S1设定2theta范围26至30°;
S2平滑一次,选择背景(Background function and Point Sampling目录下选择第三个,Cubic spline),点击Apply;
S3对Li2SiO3的(111)衍射峰(2theta=26.8±0.3°)和Si(111)衍射峰(2theta=28.4±0.3°)进行拟合,计算得到的峰面积分别记为A1和A2;
S4计算峰面积比值A2/A1。
所述X射线衍射图谱中2θ为24.7±0.2°的Li2Si2O5(111)衍射峰强度为I1,所述X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰强度为I2,计算I1/I2比值。
所述峰强度计算采用Jade 5.0对XRD结果分析步骤如下:
S1设定2theta范围23至30°;
S2平滑一次,选择背景(Background function and Point Sampling目录下选择第三个,Cubic spline),点击Apply,然后点击Remove;
S3进行自动标峰;
S4记录Li2Si2O5的(111)衍射峰(2theta=24.7±0.2°)和Li2SiO3的(111)衍射峰(2theta=26.8±0.3°)峰强分别为I1和I2;
S5计算峰强比值I1/I2。
2、扣电首次充放电性能测试:将实施例和对比例制备的锂掺杂硅氧化物复合负极材料作为活性物质,与粘结剂丙烯腈多元共聚物的水分散液(LA132,固含量15%)、导电剂(Super-P)按照70:10:20的质量比混合,加入适量的水作为溶剂调成浆料,涂覆在铜箔上,并经真空干燥、辊压,制备成负极片;以金属锂作为对电极,使用1mol/L的LiPF6三组分混合溶剂按EC:DMC:EMC=1:1:1(v/v)混合的电解液,采用聚丙烯微孔膜为隔膜,在充满惰性气体手套箱中组装成CR2032型扣式电池。扣式电池的充放电测试在武汉市蓝电电子股份有限公司的电池测试系统上进行,在常温条件,0.1C恒流嵌锂至0.01V,然后0.02C恒流嵌锂至0.005V,最后0.1C恒流脱锂至1.5V,分别取脱锂至0.8V和1.5V的容量与嵌锂容量的比值分别计算0.8V和1.5V的首次库伦效率。
其他电池性能检测按照行业通用检测方法进行。结果见表4、表5、表6。
表4对比例1至4制备的锂掺杂硅氧化物复合负极材料指标和电池性能
表5所有实施例制备的高首效锂掺杂硅氧化物复合负极材料指标和电池性能
表6对比例5至8制备的锂掺杂硅氧化物复合负极材料指标和电池性能
表4中,第1至4组分别为对比例1至4所得产品数据;表5中第1至3组为实施例1所得产品数据,第4至6组为实施例2所得产品数据,第7至9组为实施例3所得产品数据,第10至12组为实施例4所得产品数据;表6中,第1至4组分别为对比例5至8所得产品数据。
根据表4、表5、表6记载,从对比例1与实施例1-1至实施例1-3对照,可以看出,复合负极材料的A2/A1有所降低,I1/I2大幅降低,0.8V容量获得提高,首效的提高也取得了突破;从对比例2与实施例2-1至实施例2-3对照,可以看出,0.8V容量明显提高,首效的提高也取得了突破;从对比例3与实施例3-1至实施例3-3对照,可以看出,0.8V容量获得提高,首效的提高也取得了突破;从对比例4与实施例4-1至实施例4-3对照,可以看出,采用实施例4-1至实施例4-3的单组分或复合组分氧化物成核添加剂,能够更大幅度地同时提升材料电池性能中的容量和首效。从对比例5至对比例8可见,复合负极材料的组成在本发明公开范围外的,当参数为A2/A1<1.0,I1/I2<0.25时,材料电池性能中的容量和首效都比本发明提供的材料有所降低,而当A2/A1<1.0,I1/I2≥0.25时,上述两方面性能进一步降低。
本发明以特定的制备工艺步骤、参数,制备了具有特定的参数范围(I1/I2<0.25,A2/A1≥1.0)的锂掺杂硅氧化物复合负极材料,能够得到更高首效的复合负极,对此类材料在高能量密度锂离子电池中的应用具有推进作用。
以上对本发明优选的具体实施方式和实施例作了详细说明,但是本发明并不限于上述实施方式和实施例,在本领域技术人员所具备的知识范围内,还可以在不脱离本发明构思的前提下作出各种变化。
Claims (10)
1.高首效锂掺杂硅氧化物复合负极材料,其特征在于:包括纳米硅、锂硅酸盐和导电碳层,所述复合负极材料的X射线衍射图谱中2θ为24.7±0.2°的Li2Si2O5(111)衍射峰强度为I1,X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰强度为I2,I1/I2<0.25。
2.根据权利要求1所述的高首效锂掺杂硅氧化物复合负极材料,其特征在于:所述复合负极材料的X射线衍射图谱中2θ为26.8±0.3°的Li2SiO3(111)衍射峰面积为A1,X射线衍射图谱中2θ为28.4±0.3°的Si(111)衍射峰面积为A2,A2/A1≥1.0。
3.根据权利要求1所述的高首效锂掺杂硅氧化物复合负极材料,其特征在于:所述锂掺杂硅氧化物复合负极材料为核壳结构;所述核壳结构包括核层和壳层;所述核层包括纳米硅和锂硅酸盐,所述锂硅酸盐含有Li2SiO3和Li2Si2O5的一种或两种,所述壳层包括分布于核层表面的导电碳层。
4.根据权利要求1所述的高首效锂掺杂硅氧化物复合负极材料,其特征在于:所述纳米硅为单质硅,纳米硅的平均晶粒尺寸3至20nm。
5.根据权利要求1所述的高首效锂掺杂硅氧化物复合负极材料,其特征在于:所述复合负极材料的D50为2至15μm,所述复合负极材料的D90为5至25μm。
6.权利要求1至5任一项所述的高首效锂掺杂硅氧化物复合负极材料的制备方法,其特征在于:包括以下步骤:
S1、将硅氧化物SiOx、锂源和Li2SiO3成核添加剂采用固相混合方式进行混合,形成预锂前驱体;
S2、将预锂前驱体在真空或非氧化气氛下热处理,然后解聚、筛分,得到复合物粉体;
S3、对步骤S2形成的复合物粉体进行除杂改性处理,得到锂掺杂硅氧化物复合负极材料。
7.根据权利要求6所述的高首效锂掺杂硅氧化物复合负极材料的制备方法,其特征在于:各物质质量份数为:硅氧化物SiOx100份、锂源5至20份、Li2SiO3成核添加剂0.02至1份。
8.根据权利要求6所述的高首效锂掺杂硅氧化物复合负极材料的制备方法,其特征在于:所述Li2SiO3成核添加剂包括稀土金属氧化物。
9.根据权利要求6所述的高首效锂掺杂硅氧化物复合负极材料的制备方法,其特征在于:所述硅氧化物SiOx中,0.7≤x≤1.3。
10.根据权利要求6所述的高首效锂掺杂硅氧化物复合负极材料的制备方法,其特征在于:所述硅氧化物SiOx未经过碳包覆;或者,所述硅氧化物SiOx经过碳包覆,其中碳包覆的硅氧化物SiOx中的碳包覆方式为气相包覆或固相包覆中的任意一种,硅氧化物SiOx中碳包覆的质量百分数为0.1至6%。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210943730.XA CN115241436B (zh) | 2022-08-08 | 2022-08-08 | 高首效锂掺杂硅氧化物复合负极材料及其制备方法 |
US18/351,738 US20230369575A1 (en) | 2022-08-08 | 2023-07-13 | Lithium-doped silicon oxide composite anode material with high initial coulombic efficiency and preparation method thereof |
JP2023116252A JP2023134681A (ja) | 2022-08-08 | 2023-07-14 | 高初回クーロン効率のリチウムドープケイ素酸化物複合負極材料及びその製造方法 |
KR1020230096715A KR20230118529A (ko) | 2022-08-08 | 2023-07-25 | 초기 쿨롱 효율이 높은 리튬-도핑 실리콘 산화물 복합음극 재료 및 이의 제조 방법 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210943730.XA CN115241436B (zh) | 2022-08-08 | 2022-08-08 | 高首效锂掺杂硅氧化物复合负极材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115241436A true CN115241436A (zh) | 2022-10-25 |
CN115241436B CN115241436B (zh) | 2024-02-20 |
Family
ID=83678691
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210943730.XA Active CN115241436B (zh) | 2022-08-08 | 2022-08-08 | 高首效锂掺杂硅氧化物复合负极材料及其制备方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20230369575A1 (zh) |
JP (1) | JP2023134681A (zh) |
KR (1) | KR20230118529A (zh) |
CN (1) | CN115241436B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116802847A (zh) * | 2023-03-02 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | 硅基负极活性材料及其制备方法、二次电池及用电装置 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104638237A (zh) * | 2015-01-20 | 2015-05-20 | 深圳市贝特瑞新能源材料股份有限公司 | 一种锂离子电池氧化亚硅复合材料、制备方法及其用途 |
US20170117543A1 (en) * | 2015-10-26 | 2017-04-27 | Lg Chem, Ltd. | Negative electrode active particle and method for manufacturing the same |
JP2019029297A (ja) * | 2017-08-03 | 2019-02-21 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質及び非水電解質二次電池、並びに非水電解質二次電池用負極材の製造方法 |
CN109802120A (zh) * | 2019-01-24 | 2019-05-24 | 广东凯金新能源科技股份有限公司 | 一种硅碳复合材料及其制法 |
US20190319261A1 (en) * | 2016-11-30 | 2019-10-17 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode material and nonaqueous electrolyte secondary battery |
KR20200089208A (ko) * | 2019-01-16 | 2020-07-24 | 주식회사 테라테크노스 | 코어 쉘 나노와이어 기반 탄소복합 음극재 |
CN112751029A (zh) * | 2019-10-30 | 2021-05-04 | 贝特瑞新材料集团股份有限公司 | 一种硅氧复合负极材料及其制备方法和锂离子电池 |
CN112751027A (zh) * | 2019-10-30 | 2021-05-04 | 贝特瑞新材料集团股份有限公司 | 一种负极材料及其制备方法和锂离子电池 |
CN113264684A (zh) * | 2021-06-11 | 2021-08-17 | 辽宁爱尔创生物材料有限公司 | 一种牙科用硅酸锂玻璃陶瓷及其制备方法、硅酸锂玻璃陶瓷修复体 |
CN113764642A (zh) * | 2021-09-08 | 2021-12-07 | 广东凯金新能源科技股份有限公司 | 一种含锂硅氧化物复合负极材料及其制备方法和锂离子电池 |
-
2022
- 2022-08-08 CN CN202210943730.XA patent/CN115241436B/zh active Active
-
2023
- 2023-07-13 US US18/351,738 patent/US20230369575A1/en active Pending
- 2023-07-14 JP JP2023116252A patent/JP2023134681A/ja active Pending
- 2023-07-25 KR KR1020230096715A patent/KR20230118529A/ko unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104638237A (zh) * | 2015-01-20 | 2015-05-20 | 深圳市贝特瑞新能源材料股份有限公司 | 一种锂离子电池氧化亚硅复合材料、制备方法及其用途 |
US20170117543A1 (en) * | 2015-10-26 | 2017-04-27 | Lg Chem, Ltd. | Negative electrode active particle and method for manufacturing the same |
US20190319261A1 (en) * | 2016-11-30 | 2019-10-17 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode material and nonaqueous electrolyte secondary battery |
JP2019029297A (ja) * | 2017-08-03 | 2019-02-21 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質及び非水電解質二次電池、並びに非水電解質二次電池用負極材の製造方法 |
KR20200089208A (ko) * | 2019-01-16 | 2020-07-24 | 주식회사 테라테크노스 | 코어 쉘 나노와이어 기반 탄소복합 음극재 |
CN109802120A (zh) * | 2019-01-24 | 2019-05-24 | 广东凯金新能源科技股份有限公司 | 一种硅碳复合材料及其制法 |
CN112751029A (zh) * | 2019-10-30 | 2021-05-04 | 贝特瑞新材料集团股份有限公司 | 一种硅氧复合负极材料及其制备方法和锂离子电池 |
CN112751027A (zh) * | 2019-10-30 | 2021-05-04 | 贝特瑞新材料集团股份有限公司 | 一种负极材料及其制备方法和锂离子电池 |
CN113264684A (zh) * | 2021-06-11 | 2021-08-17 | 辽宁爱尔创生物材料有限公司 | 一种牙科用硅酸锂玻璃陶瓷及其制备方法、硅酸锂玻璃陶瓷修复体 |
CN113764642A (zh) * | 2021-09-08 | 2021-12-07 | 广东凯金新能源科技股份有限公司 | 一种含锂硅氧化物复合负极材料及其制备方法和锂离子电池 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116802847A (zh) * | 2023-03-02 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | 硅基负极活性材料及其制备方法、二次电池及用电装置 |
Also Published As
Publication number | Publication date |
---|---|
CN115241436B (zh) | 2024-02-20 |
KR20230118529A (ko) | 2023-08-11 |
US20230369575A1 (en) | 2023-11-16 |
JP2023134681A (ja) | 2023-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101767848B1 (ko) | 비수전해질 이차 전지용 부극재, 비수전해질 이차 전지용 부극재의 제조 방법 및 리튬 이온 이차 전지 | |
CN111180691B (zh) | 双层碳包覆的硅基复合材料及其制备方法和应用 | |
CN111072038B (zh) | 一种用于锂离子电池负极的改性一氧化硅材料及其制备方法 | |
CN112018367B (zh) | 用于电池的负极活性材料及其制备方法、电池负极、电池 | |
JP7288059B2 (ja) | シリコン酸素複合負極材料、その調製方法及びリチウムイオン電池 | |
JP5245592B2 (ja) | 非水電解質二次電池用負極材、ならびにリチウムイオン二次電池及び電気化学キャパシタ | |
CN108346788B (zh) | 一种碳包覆硅铁合金复合负极材料的制备方法 | |
CN111048770B (zh) | 一种三元掺杂的硅基复合材料及其制备方法和应用 | |
CN111477849B (zh) | 一种多孔Si/SiC/C材料的制备方法及负极材料 | |
WO2022016951A1 (zh) | 硅基负极材料、负极和锂离子电池及其制备方法 | |
JP5949194B2 (ja) | 非水電解質二次電池用負極活物質の製造方法 | |
CN111048764A (zh) | 一种硅碳复合材料及其制备方法和应用 | |
CN106414326B (zh) | 纳米硅材料及其制造方法和二次电池的负极 | |
CN111342030A (zh) | 一种多元复合高首效锂电池负极材料及其制备方法 | |
CN113764642A (zh) | 一种含锂硅氧化物复合负极材料及其制备方法和锂离子电池 | |
WO2022002057A1 (zh) | 硅氧复合负极材料、负极和锂离子电池及其制备方法 | |
CN107732164B (zh) | 钠离子电池用介孔结晶型Si-无定型SiO2-有序介孔碳复合材料的制备方法和应用 | |
CN109494399A (zh) | 一种硅/固态电解质纳米复合材料及其制备方法和应用 | |
CN113422037B (zh) | 原位转化构筑含磷酸锂包覆层的硅基复合材料及制备方法 | |
CN115241436B (zh) | 高首效锂掺杂硅氧化物复合负极材料及其制备方法 | |
CN103378355A (zh) | 碱金属二次电池及其用的负极活性物质、负极材料、负极和负极活性物质的制备方法 | |
CN111342017A (zh) | 锂离子电池用多元复合硅氧负极材料及其制备方法 | |
KR20000056339A (ko) | 리튬 이온 이차 전지 | |
CN111326727A (zh) | 一种锂离子电池用多元硅氧负极材料及其制备方法 | |
Guo et al. | Structure, Morphology, and Composition of Mn 3 N 2/MnO/C Composite Anode Materials for Li-Ion Batteries |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |