WO2023125171A1 - 负极材料及其制备方法、锂离子电池 - Google Patents
负极材料及其制备方法、锂离子电池 Download PDFInfo
- Publication number
- WO2023125171A1 WO2023125171A1 PCT/CN2022/140481 CN2022140481W WO2023125171A1 WO 2023125171 A1 WO2023125171 A1 WO 2023125171A1 CN 2022140481 W CN2022140481 W CN 2022140481W WO 2023125171 A1 WO2023125171 A1 WO 2023125171A1
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- WIPO (PCT)
- Prior art keywords
- lithium
- negative electrode
- silicon
- silicate
- electrode material
- Prior art date
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 190
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 268
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 165
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 143
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 115
- 239000011149 active material Substances 0.000 claims abstract description 101
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 134
- 229910052751 metal Inorganic materials 0.000 claims description 125
- 239000002184 metal Substances 0.000 claims description 124
- 229910052744 lithium Inorganic materials 0.000 claims description 120
- 229910052799 carbon Inorganic materials 0.000 claims description 118
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 103
- 238000005530 etching Methods 0.000 claims description 55
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 53
- 239000000126 substance Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 31
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000007790 solid phase Substances 0.000 claims description 20
- 230000001681 protective effect Effects 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 15
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 229910012573 LiSiO Inorganic materials 0.000 claims description 3
- 239000012448 Lithium borohydride Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 14
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 62
- 239000000243 solution Substances 0.000 description 54
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 29
- 238000004519 manufacturing process Methods 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 229910052710 silicon Inorganic materials 0.000 description 22
- 239000010703 silicon Substances 0.000 description 22
- 239000000395 magnesium oxide Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical group [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- 238000012546 transfer Methods 0.000 description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
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- 239000010439 graphite Substances 0.000 description 12
- 239000002210 silicon-based material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 150000004760 silicates Chemical class 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 9
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- 239000001301 oxygen Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000027756 respiratory electron transport chain Effects 0.000 description 9
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- 229910017625 MgSiO Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
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- 239000011162 core material Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
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- 239000000391 magnesium silicate Substances 0.000 description 7
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- 235000019792 magnesium silicate Nutrition 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- YJSAVIWBELEHDD-UHFFFAOYSA-N [Li].[Si]=O Chemical compound [Li].[Si]=O YJSAVIWBELEHDD-UHFFFAOYSA-N 0.000 description 6
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- 229910010100 LiAlSi Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
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- 239000005543 nano-size silicon particle Substances 0.000 description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 2
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- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 description 2
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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Definitions
- the disclosure relates to the field of lithium-ion batteries, and relates to negative electrode materials, preparation methods thereof, and lithium-ion batteries.
- Silicon oxide material is an essential negative electrode material in the development of a new generation of ultra-large capacity lithium-ion batteries.
- the silicon oxide industry has been researching and laying out the development of silicon-based lithium-ion batteries for more than ten years.
- silicon-based materials represented by silicon oxide have not been used on a large scale.
- the main factor limiting the application of silicon-based materials is the natural disadvantages of silicon-based materials themselves. High expansion and drastic volume change, low first effect, magnification, etc. are all problems that need to be solved urgently.
- Metal doping of the silicon-based core is one of the most direct improvements to improve the first-efficiency performance of silicon-based anode materials.
- inactive silicate is formed, thereby avoiding the formation of inactive lithium silicate by the interaction between active lithium and oxygen during the lithium intercalation process, and improving the first effect of silicon-oxygen materials.
- doping metals it is required to have certain reducibility, such as Li, Mg, etc.
- Lithium metal is one of the best choices.
- silicon-based materials form inactive materials such as lithium silicates of various phases inside after pre-lithiation. Outside the buffer zone in the process, the high lithium content at the interface can also act as a fast ion conductor to promote the rapid transfer of lithium ions inside.
- the pre-lithiation process has been recognized as one of the most efficient ways to improve the first effect of silicon-based materials.
- the present disclosure provides a negative electrode material, the negative electrode material includes an active material, and the active material includes a skeleton structure penetrating through the active material and a silicon oxide material embedded on the skeleton structure; the skeleton structure includes a A lithium silicate skeleton inside the active material and a water-insoluble silicate skeleton located on the surface of the active material, the water-insoluble silicate skeleton being connected to the lithium silicate skeleton;
- the intensity of the strongest diffraction characteristic peak of the lithium silicate is I A
- the intensity of the strongest diffraction characteristic peak of the water-insoluble silicate is I B
- 0.03 ⁇ IB / IA ⁇ 0.2 is 0.03 .
- the present disclosure also provides a negative electrode material, the negative electrode material including an active material
- the active material includes lithium silicate, water-insoluble silicate and silicon-oxygen material
- the water-insoluble silicate is coated on the surface of the lithium silicate
- the silicon-oxygen material is contained in the lithium silicate and/or the water-insoluble silicate,
- the intensity of the strongest diffraction characteristic peak of the lithium silicate is I A
- the intensity of the strongest diffraction characteristic peak of the water-insoluble silicate is I B
- 0.03 ⁇ IB / IA ⁇ 0.2 is 0.03 .
- the silicon-oxygen material is SiO n , where 0.5 ⁇ n ⁇ 1.5.
- the lithium silicate includes Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 4 SiO 4 , Li 2 Si 3 O 7 , Li 8 SiO 6 , Li 6 Si 2 O 7 , Li 4 Si 2 At least one of O 7 , Li 2 Si 4 O 7 and LiSiO 3 .
- the water-insoluble silicate includes zA 2 O ⁇ MO y ⁇ xSiO 2 , wherein M includes Mg, Al, Ca, Ge, Cr, V, Ti, Sc, Co, Ni, Cu, Sr , at least one of Zn, Zr, Fe and Mn, A includes at least one of Li, Na and K, 0.2 ⁇ x ⁇ 10.0, 1.0 ⁇ y ⁇ 3.0, 0 ⁇ z ⁇ 5.0.
- the water-insoluble silicate further includes A 2 O ⁇ nSiO 2 , wherein A includes at least one of Li, Na, and K, and 1 ⁇ n ⁇ 10.
- the work function range of the water-insoluble silicate is 2.5eV ⁇ 7.0eV.
- the water-insoluble silicate is located within a depth region of 20 nm to 50 nm on the surface of the active material.
- the mass content of Li element in the water-insoluble silicate is W 1 %
- the Li element content in the lithium silicate is W 2 %
- the negative electrode material further includes a carbon layer existing on the surface of the active material.
- the average thickness of the carbon layer is 30nm-500nm.
- the tap density of the negative electrode material is 0.6g/cm 3 -1.20g/cm 3 .
- the specific surface area of the negative electrode material is 1.00m 2 /g ⁇ 12.0m 2 /g.
- the average particle diameter of the negative electrode material is 3.0 ⁇ m ⁇ 12.0 ⁇ m.
- the mass percentage content of carbon in the negative electrode material is 1.5wt%-10.0wt%.
- the mass percent content of lithium in the negative electrode material is 3wt% ⁇ 15wt%.
- the pH of the negative electrode material is 8.5-12.0.
- the intensity of the strongest diffraction characteristic peak of lithium silicate is I A
- the intensity of the strongest diffraction characteristic peak of water-insoluble silicate is I B
- the lithium element content in the water-insoluble silicate of the negative electrode material is pm
- the total lithium element content of the negative electrode material is p Li , wherein 0.01 ⁇ pm/p Li ⁇ 0.6 .
- the present disclosure also provides a preparation method of negative electrode material, comprising the following steps:
- the negative electrode material is obtained by mixing the surface-etched silicon-oxygen material with a substance containing metal M and/or metal A, and performing a solid-phase thermal reaction under a protective atmosphere.
- the substance containing metal A includes: at least one of metal A simple substance, metal A carbonate, metal A oxide, and metal A hydroxide, wherein A includes Li, Na, K at least one of the
- the metal M-containing substance includes at least one of metal M simple substance, metal M carbonate, metal M oxide, and metal M hydroxide, wherein M includes Mg, Al, Ca , Ge, Cr, Pb, Sr, Zn, Zr, Fe and Mn at least one.
- the mass ratio of the silicon-oxygen material after the surface etching treatment to the substance containing metal M and/or metal A is 1:(0.01 ⁇ 0.1).
- the mass ratio of the silicon-oxygen material after the surface etching treatment to the substance containing metal M and/or metal A is 1:(0.075 ⁇ 0.1).
- the present disclosure also provides a preparation method of negative electrode material, comprising the following steps:
- the silicon-oxygen material after the surface etching treatment is mixed with the compound containing metal M, and a solid-phase thermal reaction is carried out under a protective atmosphere to obtain the negative electrode material.
- the metal M-containing compound includes at least one of metal M carbonate, metal M oxide, and metal M hydroxide, wherein M includes Mg, Al, Ca, Ge, Cr , at least one of Pb, Sr, Zn, Zr, Fe and Mn.
- the mass ratio of the silicon-oxygen material after the surface etching treatment to the compound containing the metal M is 1:(0.01 ⁇ 0.1).
- the mass ratio of the silicon-oxygen material after the surface etching treatment to the compound containing the metal M is 1:(0.075 ⁇ 0.1).
- the compound containing metal M is an oxide of metal M.
- the mixing method includes at least one of mechanical stirring, ultrasonic dispersion and grinding dispersion.
- the mixing method is ball milling, and the ball milling time is 3h-24h.
- the gas in the protective atmosphere includes at least one of nitrogen, helium, neon, argon, krypton and xenon.
- the temperature of the solid-phase thermal reaction is 600°C-1200°C.
- the time for the solid phase thermal reaction is 3h-12h.
- the heating rate of the solid-phase thermal reaction is 1° C./min ⁇ 5° C./min.
- the pre-lithiated silicon-oxygen material is a pre-lithiated carbon-coated silicon-oxygen material.
- the pre-lithiated carbon-coated silicon-oxygen material is obtained by reacting a carbon-coated silicon-oxygen material with a lithium source.
- the silicon-oxygen material is SiO n , where 0.5 ⁇ n ⁇ 1.5.
- the average particle size (D 50 ) of the silicon-oxygen material is 2.0 ⁇ m-15.0 ⁇ m.
- the thickness of the carbon layer on the surface of the carbon-coated silicon-oxygen material is 30nm-500nm.
- the lithium source includes at least one of lithium elemental substance or lithium-containing compound.
- the lithium source includes at least one of lithium hydride, lithium alkyl, lithium metal, lithium aluminum hydride, lithium amide and lithium borohydride.
- reaction temperature between the carbon-coated silicon-oxygen material and the lithium source is 150°C to 300°C.
- reaction time between the carbon-coated silicon-oxygen material and the lithium source is 2.0 hours to 6.0 hours.
- the mass ratio of the carbon-coated silicon-oxygen material to the lithium source is 1:(0.01 ⁇ 0.20).
- the mass percent content of lithium in the pre-lithiated carbon-coated silicon-oxygen material is 3wt%-20wt%.
- the method before performing surface etching treatment on the pre-lithiated silicon-oxygen material, the method further includes:
- a prelithiated silicon oxide material obtained by reacting a silicon oxide material with a lithium source
- a pre-lithiated carbon-coated silicon-oxygen material obtained by reacting a carbon-coated silicon-oxygen material with a lithium source.
- the acid solution used in the surface etching treatment has the characteristic that: when performing the surface etching treatment on the pre-lithiated silicon-oxygen material, the pH of the surface etching reaction system is kept ⁇ 7.
- the acid solution used in the surface etching treatment includes hydrochloric acid, acetic acid, nitric acid, citric acid, oxalic acid, sulfuric acid, formic acid, phenol, phosphoric acid, hydrogen phosphate, hydroiodic acid, hydrobromic acid, ethylenediaminetetra At least one of acetic acid, glycolic acid, gluconic acid, and succinic acid.
- the time for the surface etching treatment is 0.5-10.0 hours.
- the present disclosure also provides a lithium ion battery, which comprises the negative electrode material described in the above first aspect or the negative electrode material prepared according to the preparation method of the negative electrode material described in the above first aspect.
- Fig. 1 is the process flow chart of the preparation method of negative electrode material provided by the present disclosure
- FIG. 2 is a schematic structural view of the negative electrode material provided by the present disclosure
- FIG. 3 is a schematic structural view of the negative electrode material provided by the present disclosure.
- FIG. 4 is a schematic diagram of the change of the capacity retention rate of the negative electrode material prepared by the embodiment of the present disclosure and the comparative example as the number of cycles increases;
- FIG. 5 is a schematic diagram of the change in conductivity of the negative electrode material prepared in the embodiment of the present disclosure and the comparative example;
- Fig. 6 is the XRD diffraction pattern of the negative electrode material that the embodiment 3 of the present disclosure makes;
- the disclosure provides a negative electrode material, a preparation method thereof, and a lithium ion battery.
- the negative electrode material of the present disclosure can improve processing performance, have excellent electrochemical cycle and expansion inhibition performance, prolong the service life of the lithium ion battery, and reduce production costs.
- the negative electrode material includes an active material, and the active material includes a skeleton structure penetrating through the active material and a silicon-oxygen material embedded in the skeleton structure; the skeleton structure includes a lithium silicate skeleton located inside the active material And the skeleton of the water-insoluble silicate located on the surface of the active material, the skeleton of the water-insoluble silicate is connected to the skeleton of lithium silicate; Among them, in the XRD spectrum of the negative electrode material, the strongest diffraction characteristic peak of lithium silicate is The intensity is I A , the intensity of the strongest diffraction characteristic peak of the water-insoluble silicate is I B , and 0.03 ⁇ IB / IA ⁇ 0.2 .
- the range of I B /I A can be, for example, 0.05 ⁇ I B /I A ⁇ 0.2, 0.1 ⁇ I B /I A ⁇ 0.2, 0.12 ⁇ I B /I A ⁇ 0.18 or 0.14 ⁇ I B /I A ⁇ 0.16 .
- the term "skeleton” refers to the main substance (such as the weight of the main substance accounting for than the total weight of the structure is greater than or equal to 51%), in other words, it can be understood that the main substance is used as a basic substance to support, form or constitute a certain structure; for example, “the skeleton of lithium silicate” can be understood as lithium silicate is formed
- the main component of the structure of lithium silicate is the basic substance that supports, forms or constitutes the structure of lithium silicate, and the structure of lithium silicate can be dispersed/embedded with other components (such as the silicon-oxygen material disclosed herein); for example, "Skeleton of water-insoluble silicate” can be understood as, water-insoluble silicate is the main component forming the structure of water-insoluble silicate, and is the basis for supporting, forming or forming the structure of water-insoluble silicate
- the substance, the structure in which the water-insoluble silicate resides, may have other components dispersed/embedded therein (such as the
- the negative electrode material includes an active material 100;
- the active material 100 includes lithium silicate 120, water-insoluble silicate 140 and silicon-oxygen material 160;
- the water-insoluble silicate 140 is coated on the surface of the lithium silicate 120;
- the silicon-oxygen material 160 is contained in the lithium silicate 120 and/or the water-insoluble silicate 140,
- the intensity of the strongest diffraction characteristic peak of the lithium silicate is I A
- the intensity of the strongest diffraction characteristic peak of the water-insoluble silicate is I B
- 0.03 ⁇ IB / IA ⁇ 0.2 is 0.03 .
- the pre-lithiated silicon-oxygen material is etched on the surface (the material mainly includes lithium silicate 120, usually the inner core includes lithium silicate 120, and a silicon oxide layer is formed on the surface), which is non-
- the formation of water-soluble silicates leaves pores, and subsequently reacts with metal M and/or metal A-containing substances to obtain a structure of water-insoluble silicate-coated lithium silicate 120;
- the silicon-based disproportionation of the pre-lithiated silicon-oxygen material undergoes subsequent high-temperature treatment, forming a structure in which the silicon-oxygen material 160 is dispersed or embedded in the lithium silicate 120 and/or the water-insoluble silicate 140 .
- water-insoluble silicates 140 include, but are not limited to, silicates that are insoluble in polar solutions, such as aqueous solutions.
- the silicon-oxygen material (or called silicon-based active material) includes at least one of nano-silicon, silicon oxide, silicon carbide, silicon nitride, silicon sulfide or silicon alloy.
- the negative electrode material further includes a coating layer 200 covering the surface of the active material 100 .
- the silicon-oxygen material (or silicon-based active material, including nano-silicon, silicon oxide, silicon carbide, silicon nitride, silicon sulfide or silicon alloy, etc.) Skeleton) structure
- the outer water-insoluble silicate and the inner lithium silicate are silicates of different crystal forms grown on the same silicon-oxygen skeleton, and the silicates of two different materials are connected, which is beneficial to
- the electrochemical performance of the active material can quickly carry out electron transfer and deintercalation of lithium, which is conducive to reducing the internal resistance of the material and improving the lithium ion transfer ability.
- the encapsulation of the silicon-oxygen material by the skeleton of the water-insoluble silicate located on the outer layer can effectively prevent the contact of water with the strong alkaline lithium silicate and inhibit the hydrolysis of lithium silicate, thereby effectively improving the gas production of the material and realizing the protection of the material. pH control to improve processing performance.
- the lithium silicate in the inner layer and the water-insoluble silicate in the outer layer are closely connected through silicon and silicon-oxygen materials. The difference in work function of the two silicate materials leads to the formation of a heterojunction interface between the two, which can Improve electron transfer efficiency, thereby increasing lithium intercalation depth, improving capacity and cycle performance.
- Lithium silicate and water-insoluble silicate are silicates of different crystal forms grown on the same silicon-oxygen skeleton, which can form a tight heterojunction interface without forming a vacuum section, which is beneficial to the electron exchange between heterojunction materials.
- the transfer realizes the effective conduction of lithium ions through the skeleton structure and the silicon-oxygen material on the surface of the active material, which improves the ionic conductivity of the material and is conducive to the exertion of the rate performance of the material.
- the silicon-oxygen material is SiO n , where 0.5 ⁇ n ⁇ 1.5.
- the silicon-oxygen material may be SiO n such as SiO 0.5 , SiO 0.8 , SiO 0.9 , SiO, SiO 1.1 , SiO 1.2 or SiO 1.5 and so on.
- the silicon-oxygen material is SiO. It can be understood that the composition of SiO n is relatively complex, and it can be understood that it is formed by uniformly dispersing nano-silicon in SiO 2 .
- the silicon-oxygen material can include at least two kinds of simple silicon, silicon dioxide, and silicon oxide.
- lithium silicate includes Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 4 SiO 4 , Li 2 Si 3 O 7 , Li 8 SiO 6 , Li 6 Si 2 O 7 , Li At least one of 4 Si 2 O 7 , Li 2 Si 4 O 7 and LiSiO 3 .
- the lithium metal is embedded in the silicon-oxygen framework, showing a lithium silicate framework structure.
- lithium silicate includes Li 2 O ⁇ mSiO 2 , where m satisfies 0 ⁇ m ⁇ 2, for example, m can be 0.1, 0.3, 0.5, 0.7, 0.9, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8 or 2.
- the water-insoluble silicate includes zA 2 O ⁇ MO y ⁇ xSiO 2 , wherein M includes Mg, Al, Ca, Ge, Cr, V, Ti, Sc, Co, Ni, At least one of Cu, Sr, Zn, Zr, Fe, and Mn, A includes at least one of Li, Na, and K, 0.2 ⁇ x ⁇ 10.0, 1.0 ⁇ y ⁇ 3.0, 0 ⁇ z ⁇ 5.0. It should be noted that metal A and/or metal M are embedded in the silicon-oxygen framework to form a framework structure of water-insoluble silicate.
- the water-insoluble silicate further includes A 2 O ⁇ nSiO 2 , wherein A includes at least one of Li, Na, and K, and 1 ⁇ n ⁇ 10.
- the water-insoluble silicate may include but not limited to Mg 2 SiO 4 , Al 2 SiO 5 , CaSiO 3 , LiAlSiO 4 , LiAlSiO, LiAlSi 2 O 6 , LiAlSi 3 O 8 , Li 2 MgSiO 4 , MgSiO 3 , or Li 2 CaSiO 4 .
- the optional work function range of the water-insoluble silicate is 2.5eV ⁇ 7.0eV, optionally 4.50eV ⁇ 6.5eV, which can be guaranteed On the basis of processing performance, it is beneficial to improve the electron transfer efficiency and greatly improve the conductivity of the powder. It can be understood that the appropriate work function range can make the electron transfer efficiency between heterojunctions higher.
- the skeleton of the water-insoluble silicate is used as the outer skeleton and is in direct contact with the conductive carbon layer, and its work function needs to be higher than that of the carbon layer.
- the work function is lower than that of lithium silicate, which is more conducive to the transfer of electrons from the outer layer to the inner layer and improves the conductivity.
- the water-insoluble silicate is located in the depth region of 20nm to 50nm on the surface of the active material, such as 25nm to 45nm, 28nm to 38nm or 30nm to 35nm, such as 20nm, 24nm, 26nm, 28nm, 30nm , 34nm, 36nm, 38nm, 40nm, 44nm, 46nm, 48nm, 50nm, or the interval value between any two endpoints above. That is, the water-insoluble silicate is located in the radial direction from the surface of the active material to a depth of, for example, 20nm to 50nm.
- the skeleton of the water-insoluble silicate is distributed in the non-water-soluble silicate.
- the surface layer structure composed of silicon-oxygen materials on the skeleton of the water-soluble silicate can prevent the electrolyte from entering the interior of the active material, prevent water from contacting with the strong alkali lithium silicate, and effectively inhibit the hydrolysis of lithium silicate.
- the skeleton of the water-insoluble silicate is connected with the lithium silicate skeleton to form a heterojunction structure.
- the silicon-oxygen material is embedded in the skeleton structure, and the skeleton of the water-insoluble silicate and the lithium silicate skeleton are connected in series through the silicon-oxygen material, so that the two skeletons are connected to form an obvious heterojunction.
- This heterojunction is composed of lithium silicate and water-insoluble silicate, both of which are grown through the common SiO2 skeleton reaction, so the interface is closely connected and continuous without forming a vacuum section, which is beneficial Electron transfer between heterojunction materials.
- this heterojunction can promote the transfer of electrons in the active material and improve the conductivity.
- the conductivity of the active material can be effectively improved, the first effect of the material can be improved, hydrolysis can be inhibited, and pH can be controlled.
- the intensity of the diffraction characteristic peak of lithium silicate is I A
- the intensity of the diffraction characteristic peak of water-insoluble silicate is I B
- 0.03 ⁇ IB /IA ⁇ 0.20 the intensity of the diffraction characteristic peak of water-insoluble silicate
- the electron transport ability can be maximized by means of the heterojunction, and the electron conductivity can reach more than 15 S/cm, which is conducive to the exertion of the rate performance of the material.
- 0.12 ⁇ IB / IA ⁇ 0.18, so as to ensure the high conductivity of the silicon-based material under the condition of ensuring the processability.
- the intensity of the diffraction characteristic peak of the water-insoluble silicate is I c
- the intensity of the diffraction characteristic peak of the lithium silicate inside the active material is I
- the intensity of the diffraction characteristic peak of the treated water-insoluble silicate is ID , and 0.03 ⁇ (I C -ID )/2I ⁇ 0.2 .
- the acid solution is sulfuric acid, hydrochloric acid, nitric acid, aqua regia, etc.
- the water-insoluble silicate is water-insoluble lithium silicate
- the ratio of (I C -ID )/2I it is also possible to achieve the strongest electron transport ability by virtue of the heterojunction, thereby effectively utilizing the material Excellent rate performance ensures high conductivity of silicon-based materials.
- the mass content of the Li element in the water-insoluble silicate on the surface of the active material is W 1 %, and the Li element content in the lithium silicate inside the active material is W 2 %, W 2 >W 1 ⁇ 0. That is, the Li element concentration on the surface of the active material is lower than the Li element concentration inside the active material.
- Lithium silicate is mainly located inside the active material, while the non-water-soluble silicate is located on the outer layer of the active material.
- the silicon-oxygen material covered by the skeleton of the non-water-soluble silicate can prevent the electrolyte from entering the interior of the active material and prevent water from entering the active material.
- Contact with strong alkali lithium silicate can effectively inhibit the hydrolysis of lithium silicate, achieve pH regulation, and inhibit gas production.
- the negative electrode material further includes a carbon layer formed on the surface of the active material. It can be understood that the skeleton of the water-insoluble silicate on the surface of the active material and the silicon-oxygen material embedded therein can directly contact the carbon layer, which can ensure the stability of the conductive channel and the lithium ion transport channel inside the particle.
- the material of the carbon layer is selected from at least one of hard carbon, soft carbon, carbon nanotubes, carbon nanofibers, graphite and graphene.
- the average thickness of the carbon layer is 30nm-500nm, optionally, the thickness of the carbon layer can be, for example, 60nm-450nm, 120nm-350nm or 220nm-320nm, such as 30nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, or an interval value between any two endpoints above, the thickness of the carbon layer is not limited to the listed values, and other unlisted values within the range of values are also applicable.
- the thickness of the carbon layer in the present disclosure is within the above range, which is conducive to improving the transmission efficiency of lithium ions, and at the same time, it is beneficial to charge and discharge the material at a large rate, effectively ensuring the comprehensive performance of the negative electrode material; at the same time ensuring the conductivity of the negative electrode material and possessing the volume of the material Swell inhibition, maintain the long-term cycle performance of the negative electrode material.
- the mass percentage content of carbon in the negative electrode material is 1.5wt% to 10wt%, optionally, it can be, for example, 2.0wt% to 8.0wt%, 4.0wt% ⁇ 7.0wt% or 5.0wt% ⁇ 6.0wt%, such as 1.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5 wt%, 9wt% or 10wt%, etc., or an interval value between any two endpoints above, but the mass percentage of carbon is not limited to the listed values, and other unlisted values within this range are also applicable.
- the mass percentage content of lithium in the negative electrode material is 3wt% ⁇ 15wt%, alternatively, the mass percentage content of lithium can be for example 4wt% ⁇ 14wt%, 6wt% ⁇ 12wt% or 8wt% ⁇ 10wt%, such as 3wt%, 3.5wt%, 4.5wt%, 5.5wt%, 8wt%, 9.5wt%, 10.5wt%, 12.1wt%, 12.9wt% or 15wt%, etc., or the interval value between any two endpoints above, but lithium The mass percentage of is not limited to the listed numerical values, and other unlisted numerical values within the numerical range are also applicable.
- the lithium content of the negative electrode material is within the above range, ensuring that most of the lithium source enters the interior of the silicon-oxygen material to form a lithium silicate skeleton (that is, lithium silicate 120), which improves the high initial Coulombic efficiency of the negative electrode material.
- the lithium silicate selected above can control the amount of lithium in the surface layer, reduce the loss of lithium after surface treatment, improve the utilization rate, and ensure that the skeleton of silicate in the surface layer of the active material can be formed during lithium doping (that is, non- Water-soluble silicate 140), and has the characteristics of water insolubility, thereby effectively hindering the contact between water and strong alkali lithium silicate (that is, lithium silicate 120), effectively inhibiting the hydrolysis of lithium silicate, exerting pH control, and inhibiting the effect of gas production effect.
- the specific surface area of the negative electrode material is 1.0m 2 /g-12.0m 2 /g; it can be, for example, 2.0m 2 /g-10.0m 2 /g, 3.5m 2 /g-6.0m 2 /g or 4.0m 2 /g ⁇ 5.5m 2 /g, such as 1.0m 2 /g, 1.50m 2 /g, 2.00m 2 /g, 3.00m 2 /g, 4.00m 2 /g, 5.0m 2 /g, 7.0m 2 /g, 9.0m 2 /g, 10.0m 2 /g or 12.0m 2 /g, etc., or the interval value between any two endpoints above, but not limited to the listed values, other unlisted values within the range Numerical values also apply.
- the specific surface area of the negative electrode material is within the above range, which ensures the processing performance of the material, is conducive to improving the first-time efficiency of the lithium battery made of the negative electrode material, and is beneficial to improving the cycle performance of the
- the average particle size of the negative electrode material is 3.0 ⁇ m to 12.0 ⁇ m, which can be, for example, 4.0 ⁇ m to 11.0 ⁇ m, 5.0 ⁇ m to 10.0 ⁇ m or 6.0 ⁇ m to 8.0 ⁇ m, such as 3.0 ⁇ m, 4.0 ⁇ m, 6.5 ⁇ m, 7.0 ⁇ m, 8.2 ⁇ m, 9.5 ⁇ m, 10.0 ⁇ m or 12.0 ⁇ m, etc., or the interval value between any two endpoints above.
- the average particle size of the negative electrode material is controlled within the above range, which is beneficial to the improvement of the cycle performance of the negative electrode material.
- the average particle size of the negative electrode material is 4.5 ⁇ m ⁇ 9.0 ⁇ m.
- the tap density of the negative electrode material is 0.6g/cm 3 to 1.2g/cm 3 ; g/cm 3 or 0.9g/cm 3 ⁇ 1.0g/cm 3 , such as 0.6g/cm 3 , 0.7g/cm 3 , 0.75g/cm 3 , 0.8g/cm 3 , 0.85g/cm 3 , 0.9g /cm 3 , 0.95g/cm 3 , 1.0g/cm 3 , 1.1g/cm 3 or 1.2g/cm 3 , etc., or the interval value between any two endpoints above, but not limited to the listed
- the numerical value of , other unlisted numerical values in this numerical range are also applicable. If the tap density of the negative electrode material is within the above range, it is beneficial to improve the energy density of the lithium battery made of the negative electrode material.
- the pH value of the negative electrode material is 8.5-12.0, which can be, for example, 8.6-11.0, 9.0-10.5 or 9.5-10.0, such as 8.5, 8.8, 8.9, 9.2, 9.5, 9.8, 10.0, 10.3, 10.5, 10.8, 11.0, 12.0, etc. , or an interval value between any two of the above endpoints. It can be understood that filling the carbon material with lithium-containing compounds can effectively reduce the alkalinity of the material, improve the processing performance of the material in water system, and improve the first effect of the negative electrode material.
- the lithium element content in the water-insoluble silicate of the negative electrode material is pm, and the total lithium element content of the negative electrode material is p Li , where 0.01 ⁇ pm/p Li ⁇ 0.6 is satisfied. It is found in the present disclosure that the content of lithium element in the negative electrode material is distributed within the above range, which can further ensure the formation of a stable water-insoluble silicate skeleton (ie, water-insoluble silicate 140) on the surface of the active material, thereby effectively preventing water and strong Alkali lithium silicate (that is, lithium silicate 120) contact can effectively inhibit the hydrolysis of lithium silicate, achieve pH regulation, and inhibit gas production.
- a stable water-insoluble silicate skeleton ie, water-insoluble silicate 140
- Alkali lithium silicate that is, lithium silicate 120
- the negative electrode material is a silicon-oxygen composite material.
- One embodiment of the present disclosure provides a method for preparing an anode material, comprising the following steps:
- the negative electrode material includes an active material, and the active material includes a skeleton structure running through the active material and a silicon-oxygen material distributed on the skeleton structure; the skeleton structure includes a lithium silicate skeleton inside the active material and a water-insoluble silicate on the surface of the active material The skeleton of the water-insoluble silicate is connected with the lithium silicate skeleton.
- the substance containing metal M reacts with the etched silicon-oxygen material in the solid state, so that the surface of the etched silicon-oxygen material forms Water-insoluble silicate can effectively isolate soluble strong alkaline substances such as lithium silicate from dissolving in the slurry, resulting in pH out of control, inhibiting the gas production of the slurry, and preventing the loss of active silicon-oxygen materials and active lithium, and improving the quality of materials.
- lithium silicate and water-insoluble silicate are silicates of different crystal forms grown on the same silicon-oxygen skeleton, which can form a tight heterojunction interface without forming a vacuum section, which is conducive to heterogeneity
- the electron transfer between the junction materials improves the ionic conductivity of the material, which is conducive to the exertion of the rate performance of the material, and the whole preparation process is simple, which is conducive to mass production and reduces costs.
- the preparation method also includes:
- carbon coating is carried out on the silicon-oxygen material, because the carbon coating layer is relatively loose and there are a large number of micropores, and the subsequent lithium source can penetrate through the carbon coating through the micropores of the carbon coating layer. layer and react on the surface of the silicon-oxygen material, and in the final negative electrode material obtained, the carbon coating layer is still located in the outermost layer.
- carbon coating includes carbon coating in gas phase and/or carbon coating in solid phase.
- the temperature of the silicon-oxygen material is raised to 600° C.-1000° C. under a protective atmosphere, and an organic carbon source gas is introduced, kept for 0.5-10 hours and then cooled.
- the organic carbon source gas includes hydrocarbons.
- the source of organic carbon includes hydrocarbons.
- hydrocarbons include alkanes, alkenes, alkynes, aromatics.
- the hydrocarbons are hydrocarbons gasifiable at 600°C to 1000°C.
- the hydrocarbons include at least one of methane, ethylene, acetylene, and benzene.
- the hydrocarbons include at least one of organic carbon sources such as methane, ethane, propane, ethylene, propylene, acetylene, benzene, or toluene.
- the carbon source includes at least one of hard carbon, soft carbon, carbon nanotubes, carbon nanofibers, graphite, graphene, pitch, and organic-inorganic hybrid carbon materials.
- the preparation method also includes:
- a prelithiated silicon oxide material obtained by reacting a silicon oxide material with a lithium source
- the carbon-coated silicon-oxygen material is reacted with a lithium source to obtain a pre-lithiated carbon-coated silicon-oxygen material.
- the silicon-oxygen material is SiO n , wherein, 0.5 ⁇ n ⁇ 1.5, SiO n can be SiO 0.5 , SiO 0.6 , SiO 0.7 , SiO 0.8 , SiO 0.9 , SiO, SiO 1.1 , SiO 1.2 or SiO 1.5 etc., for example.
- the silicon-oxygen material is SiO.
- the average particle size (D 50 ) of the silicon-oxygen material is 2.0 ⁇ m-15.0 ⁇ m; it can be, for example, 3.0 ⁇ m-13.0 ⁇ m, 6.0 ⁇ m-11.0 ⁇ m or 7.0 ⁇ m-10.0 ⁇ m, such as 2.0 ⁇ m, 3.5 ⁇ m, 4.0 ⁇ m, 4.5 ⁇ m, 5.0 ⁇ m, 5.5 ⁇ m, 6.0 ⁇ m, 7.5 ⁇ m, 9.0 ⁇ m, 10.5 ⁇ m, 12 ⁇ m or 15.0 ⁇ m, etc., or an interval value between any two endpoints above.
- the average particle size of the silicon-oxygen material in the present disclosure is within the above range, which can further ensure the structural stability, thermal stability and long-term cycle stability of the negative electrode material.
- the average particle size (D 50 ) of the carbon-coated silicon oxide material is 2.0 ⁇ m-15.0 ⁇ m; it may be, for example, 3.0 ⁇ m-13.0 ⁇ m, 6.0 ⁇ m-11.0 ⁇ m or 7.0 ⁇ m-10.0 ⁇ m, such as 2.0 ⁇ m, 3.5 ⁇ m, 4.0 ⁇ m, 4.5 ⁇ m, 5.0 ⁇ m, 5.5 ⁇ m, 6.0 ⁇ m, 7.5 ⁇ m, 9.0 ⁇ m, 10.5 ⁇ m, 12 ⁇ m or 15.0 ⁇ m, etc., or the interval value between any two of the above endpoint values, but It is not limited to the listed values, and other unlisted values within the range of values are also applicable.
- the carbon-coated silicon-oxygen material or the particle size of the silicon-oxygen material is controlled within the above range, which can avoid the problem of cycle stability caused by the type and uneven distribution of lithiated silicate products, and is conducive to improving the negative electrode material. Structural stability, thermal stability and long-term cycle stability.
- the thickness of the carbon layer on the surface of the carbon-coated silicon-oxygen material is 30nm-500nm, which can be, for example, 50nm-550nm, 90nm-500nm, 160nm-400nm or 220nm-300nm, such as 30nm, 50nm, 60nm, 70nm, 80nm , 90nm, 100nm, 150nm, 200nm, 300nm, 400nm or 500nm, or the interval value between any two endpoints above, but not limited to the listed values, other unlisted values within the range are also applicable.
- the coating layer is too thick, the lithium ion transmission efficiency will decrease, which is not conducive to the high-rate charge and discharge of the material, and the overall performance of the negative electrode material will be reduced. If the coating layer is too thin, it is not conducive to increasing the conductivity of the negative electrode material and affecting the volume of the material. The swelling inhibition performance is weak, resulting in poor long-cycle performance.
- the lithium source includes simple lithium, lithium-containing compounds or mixtures thereof.
- the lithium source includes at least one of lithium hydride, alkyllithium, metal lithium, lithium aluminum hydride, lithium amide and lithium borohydride.
- the lithium source also includes lithium-containing oxides, lithium-containing hydrides, and the like.
- the carbon-coated silicon-oxygen material or the reaction temperature of the silicon-oxygen material and the lithium source is 150°C to 300°C, for example, 180°C to 280°C, 200°C to 260°C or 210°C to 240°C, such as 150°C °C, 170°C, 180°C, 200°C, 220°C, 250°C, 280°C or 300°C, etc., or an interval value between any two endpoints above.
- the reaction time is 2.0h ⁇ 6.0h, which can be 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h or 6.0h, etc., or the interval between any two endpoints above value.
- At least part of the lithium source enters the interior of the silicon-oxygen material particles to form a Li-SiO material, and most of the lithium source is deposited on the surface of the silicon-oxygen material and undergoes a reduction reaction with the silicon-oxygen material to generate lithium oxide or hydrogen.
- Lithium oxide, these lithium oxides or lithium hydroxides are embedded in the pores of the carbon coating layer on the surface of the silicon-oxygen material.
- the mass ratio of the carbon-coated silicon-oxygen material SiO n to the lithium source is 1:(0.01-0.20), optionally, for example, 1:(0.02-0.18), 1:( 0.04 ⁇ 0.16) or 1:(0.08 ⁇ 0.12), such as 1:0.01, 1:0.03, 1:0.05, 1:0.1, 1:0.15, 1:0.2, etc., or the interval between any two endpoints above Values, but not limited to the listed values, other unlisted values within the value range are also applicable.
- the mass percent content of lithium in the pre-lithiated carbon-coated silicon-oxygen material is 3 wt % to 20 wt %.
- the present disclosure found that the lithium content in the pre-lithiated carbon-coated silicon-oxygen material in the present disclosure is within the above range, which can ensure the effective generation of water-insoluble silicate with high stability, thereby preventing the electrolyte from entering the active material. Effectively suppress gas production.
- the mass percent content of lithium in the pre-lithiated carbon-coated silicon-oxygen material can be, for example, 4wt%-18wt%, 6wt%-16wt%, or 9wt%-14wt%, such as 3wt%, 5wt%, 8wt% %, 10wt%, 12wt%, 15wt%, 18wt% or 20wt%, etc., or the interval value between any two endpoints above, but not limited to the listed values, other unlisted values within the range of values are the same Be applicable.
- the pre-lithiated silicon oxide material or the pre-lithiated carbon-coated silicon oxide material may be surface-etched by pickling.
- the acid solution used in the surface etching treatment has the following characteristics: when performing the surface etching treatment on the pre-lithiated silicon-oxygen material, the pH of the reaction system of the surface etching is maintained ⁇ 7.
- the acid solution used in the surface etching treatment includes but is not limited to hydrochloric acid, acetic acid, nitric acid, citric acid, oxalic acid, sulfuric acid, formic acid, phenol, phosphoric acid, hydrogen phosphate, hydroiodic acid, hydrogen bromide acid, ethylenediaminetetraacetic acid, glycolic acid, gluconic acid, succinic acid at least one.
- the time for the surface etching treatment is 0.5-10.0 hours.
- the surface layer of the silicon-oxygen material is mainly silicon-oxygen material and contains disproportionated silicon dioxide.
- the silicon dioxide skeleton exposed on the surface of the silicon-oxygen material after the surface etching treatment reacts with the metal M-containing substance to form a water-insoluble silicate.
- the metal M-containing substance includes M metal simple substance and/or a metal M-containing compound, and the metal M-containing compound includes metal M carbonate, metal M oxide, and metal M hydrogen At least one of oxides and soluble silicates of metal M, wherein M is selected from at least one of Mg, Al, Ca, Ge, Cr, Pb, Sr, Zn, Zr, Fe and Mn.
- the material containing metal M can be an oxide of M, such as magnesium oxide, calcium oxide, aluminum oxide, etc.
- the material containing metal M can be a carbonate of metal M, such as magnesium carbonate, calcium carbonate, aluminum carbonate .
- a simple substance containing metal M wherein M is selected from at least one of Mg, Al, Ca, Ge, Cr, Pb, Sr, Zn, Zr, Fe and Mn.
- the aforementioned metal M and metal A are respectively selected from metal elements with an electronegativity of 1.0-1.9.
- the substance containing metal M is metal M oxide.
- the substance containing metal A includes: at least one of metal A simple substance, metal A carbonate, metal A oxide, and metal A hydroxide, wherein A includes Li, At least one of Na and K.
- the metal A is at least one selected from Li, Na, and K.
- the metal A-containing compound includes at least one of metal A carbonate, metal A oxide, metal A hydroxide, and metal A soluble silicate, wherein, Exemplarily, the compound containing metal A can be an oxide of A, such as lithium oxide, potassium oxide, sodium oxide, etc.; the compound containing metal A can be a carbonate of metal A, such as lithium carbonate, potassium carbonate, sodium carbonate , wherein metal salts with strong alkalinity (such as pH>10) such as lithium carbonate, sodium carbonate, and potassium carbonate can be used in doping, and cannot be used alone.
- metal salts with strong alkalinity such as pH>10
- the mass ratio of the silicon-oxygen material after the surface etching treatment to the metal M-containing compound is 1: (0.01-0.1), optionally 1: (0.075 ⁇ 0.1).
- the disclosure found that when the mass ratio is too high, excessive insoluble inactive MO xSiO 2 is generated on the surface, 0.2 ⁇ x ⁇ 10.0, which will lead to a decrease in the reversible capacity of the powder and a decrease in electrical conductivity; when the mass ratio is too low, it means that the metal M If the content of the substance is too small, the substance containing metal M cannot fully react with the silicon-oxygen material, which is not conducive to the formation of a water-insoluble silicate skeleton on the surface of the silicon-oxygen material, resulting in the electrolyte easily passing through the surface of the negative electrode material and the particle interior. The reaction of lithium silicate is not conducive to inhibiting the alkalinity of the material, which makes the negative electrode material produce serious gas during the processing process, and the first efficiency and cycle stability of the battery decrease.
- the mass ratio of the silicon-oxygen material after the surface etching treatment to the simple substance or compound containing metal A is 1: (0.01-0.1), and it is also found in the present disclosure that the insoluble and non-active A 2 O ⁇ nSiO 2 , 1 ⁇ n ⁇ 10, in the above ratio range of the present disclosure, it can ensure the high inverse capacity and high conductivity of the powder, so that the compound of metal A can fully react with the silicon-oxygen material, which is beneficial to the silicon-oxygen
- the surface layer of the material forms a skeleton of water-insoluble silicate to avoid the reaction between the electrolyte and the lithium silicate inside the particles, thereby effectively inhibiting the alkalinity of the material and preventing the negative electrode material from producing gas during processing, thereby further improving the first efficiency and cycle of the battery stability.
- the mass ratio of the silicon-oxygen material after surface etching treatment to the substance containing metal M may be, for example, 1:(0.020-0.095), 1:(0.040-0.090), 1:(0.060-0.085) or 1 : (0.078 ⁇ 0.082), such as 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.075, 1:0.081, 1:0.083, 1: 0.085, 1: 0.087, 1: 0.091, 1: 0.093, 1: 0.095 or 1: 0.1, etc., or the interval value between any two endpoints above, but not limited to the listed values, within the value range Other values not listed also apply.
- the mass ratio of the silicon-oxygen material after the surface etching treatment to the simple substance or compound containing metal A can be, for example, 1:(0.020-0.095), 1:(0.040-0.090), 1:(0.060-0.085) Or 1: (0.078 ⁇ 0.082), such as 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.075, 1:0.081, 1:0.083, 1:0.085, 1:0.087, 1:0.091, 1:0.093, 1:0.095 or 1:0.1, etc., or the interval value between any two endpoints above, but not limited to the listed values, the value Other unrecited values within the range also apply.
- the mixing method includes at least one of mechanical stirring, ultrasonic dispersion, and grinding dispersion.
- the mixing method is not limited to the above-mentioned method, and any method that can uniformly mix the pre-lithiated silicon-oxygen material and the material containing the metal M is fine.
- the mixing method is ball milling, and the ball milling time is 3h-24h; it can be, for example, 6h-21h, 9h-17h or 11h-15h, such as 3h, 4h, 5h, 6h, 8h, 12h, 16h, 18h, 20h Or 24h, etc., or the interval value between any two endpoints above, but not limited to the listed values, other unlisted values within the range of values are also applicable. It can be understood that sufficient ball milling can make the metal M-containing substance evenly adhere to the surface of the silicon-oxygen material after surface etching treatment or the surface of carbon-coated silicon-oxygen material after surface etching treatment.
- the protective atmosphere includes at least one of nitrogen, helium, neon, argon, krypton and xenon.
- the solid-phase thermal reaction is a calcination process, and the calcination can be performed in a calcination furnace so that the calcination can be fully performed.
- the temperature of the solid phase thermal reaction is 600°C to 1200°C, for example, 640°C to 1160°C, 720°C to 920°C or 780°C to 820°C, such as 600°C, 700°C, 750°C, 800°C . Values not listed are also applicable, and 750°C to 1150°C is optional. It can be understood that when the reaction temperature is too high, the reaction will be violent, and the silicon grains will grow rapidly, which will affect the cycle performance of the material; Salt skeleton cannot be generated.
- the solid-phase thermal reaction time is 3h-12h, for example, it can be 5h-11h, 6h-9h or 7h-8h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h etc., or an interval value between any two endpoints above, but not limited to the listed values, other unlisted values within the range are also applicable.
- the skeleton of water-insoluble silicate can be formed on the surface layer of the silicon-oxygen material after surface etching treatment by sufficient calcination.
- the heating rate of the solid-phase thermal reaction is 1°C/min to 5°C/min, for example, it can be 1°C/min, 2°C/min, 3°C/min, 4°C/min or 5°C/min, etc. , or an interval value between any two endpoints above, but not limited to the listed values, other unlisted values within the range are also applicable.
- the substance containing metal M reacts with the silicon dioxide skeleton exposed by the disproportionation on the surface of the silicon-oxygen material after the surface etching treatment and the strong alkaline lithium silicate to form a water-insoluble silicate.
- the skeleton prevents the electrolyte from easily passing through the surface of the negative electrode material and reacting with the lithium silicate inside the particle, which can reduce the pH value of the material, thereby affecting the pH value of the entire negative electrode slurry, improving the processing stability of the pre-lithium material, and making the negative electrode The first effect of the material is improved.
- step S20 the method further includes:
- the average particle size of the negative electrode material is 1 ⁇ m to 10 ⁇ m, such as 2.5 ⁇ m to 9.5 ⁇ m, 3.5 ⁇ m to 7 ⁇ m, or 4.5 ⁇ m to 6.5 ⁇ m, such as 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m or 10 ⁇ m, etc., or the interval value between any two endpoint values mentioned above.
- the average particle size of the negative electrode material is controlled within the above range, which is beneficial to the improvement of the cycle performance of the negative electrode material.
- the average particle diameter of the negative electrode material is 4 ⁇ m ⁇ 7 ⁇ m.
- sieving includes at least one of crushing, ball milling, screening, or classifying.
- the negative electrode material prepared by the above preparation method can hinder the reaction between the strong alkaline material and the solvent, suppress the gas production, and reduce the impact on the material at the same time.
- the influence of capacity first effect realizes the control of the pH value of the negative electrode slurry made of this material.
- the active silicon-oxygen material can remain embedded in the silicate skeleton and the lithium silicate skeleton, and the formed skeleton structure can stabilize and play an expansion buffer role, so that nano-silicon crystal grains are embedded in the entire particle system, making the silicon-oxygen material It can maintain good contact with the conductive carbon layer, realize the improvement of conductivity, reduce the interface impedance, and ensure the stability of the conductive channel and lithium ion transmission channel inside the particle.
- an embodiment of the present disclosure provides a method for preparing an anode material, comprising the following steps:
- the silicon-oxygen material after the surface etching treatment can also be additionally mixed with a substance containing metal A, and metal A includes alkali metal elements.
- metal A includes at least one of Li, Na and K kind.
- the present disclosure provides a lithium ion battery, which includes the negative electrode material of the first aspect above or the negative electrode material prepared by the preparation method of the second aspect above.
- the silicon-oxygen material is embedded in the skeleton structure, and the skeleton of the water-insoluble silicate on the outer layer is connected to the lithium silicate skeleton inside, which is beneficial to the electrochemical performance of the active material and rapidly conducts electrons.
- the transfer and deintercalation of lithium is beneficial to reduce the internal resistance of the material and improve the transfer capacity of lithium ions.
- the encapsulation of the silicon-oxygen material by the skeleton of the water-insoluble silicate located on the outer layer can effectively prevent the contact of water with the strong alkaline lithium silicate and inhibit the hydrolysis of lithium silicate, thereby effectively improving the gas production of the material and realizing the protection of the material. pH control to improve processing performance.
- the lithium silicate in the inner layer and the water-insoluble silicate in the outer layer are closely connected through silicon and silicon-oxygen materials.
- the difference in work function of the two silicate materials leads to the formation of a heterojunction interface between the two, which can Improve electron transfer efficiency, thereby increasing lithium intercalation depth, improving capacity and cycle performance.
- the pre-lithiated silicon-oxygen material is subjected to surface etching treatment, and the material containing metal M is reacted with the silicon-oxygen material after etching in solid state, so that the etched
- the surface of the silicon oxide material after etching forms a non-water-soluble silicate, which can effectively isolate soluble strong alkaline substances such as lithium silicate from dissolving in the slurry, resulting in pH out of control, inhibiting the gas production of the slurry, and preventing active silicon oxide
- the loss of materials and active lithium improves the first-effect capacity of materials; lithium silicate and water-insoluble silicate are silicates of different crystal forms grown on the same silicon-oxygen skeleton, which can form a tight heterojunction interface, without A vacuum section will be formed, which is conducive to electron transfer between heterojunction materials, improves the ionic conductivity of the material, and is conducive to the exertion of the rate performance of the material, and
- the structural representation of the negative electrode material prepared in the present embodiment is with reference to Fig. 3, and it comprises active material 100 and the carbon layer (that is cladding layer 200) that is formed on the surface of active material, and active material 100 comprises framework structure and the silicon embedded on framework structure Oxygen material;
- the skeleton structure includes a lithium silicate skeleton (i.e. lithium silicate 120) inside the active material and a magnesium silicate skeleton (i.e. water-insoluble silicate 140) on the surface of the active material, a magnesium silicate skeleton (i.e. water-insoluble Lithium silicate 140) is connected to the lithium silicate skeleton.
- the lithium silicate skeleton i.e.
- lithium silicate 120) in this embodiment is Li 2 Si 2 O 5 , Li 2 SiO 3 , Li 4 SiO 4 , and the surface layer of the active material (i.e. water-insoluble silicate 140) is Mg 2 SiO 4 and Li 2 MgSiO 4 .
- the average particle diameter (D 50 ) of the negative electrode material is 5.0 ⁇ m, the tap density is 0.98g/cm 3 , the specific surface area is 2.54m 2 /g, the mass percentage content of lithium in the negative electrode material is 9.5wt%, the carbon layer The thickness is 183nm.
- the structural representation of the negative electrode material prepared in the present embodiment is with reference to Fig. 3, and it comprises active material 100 and the carbon layer (that is cladding layer 200) that is formed on the surface of active material, and active material 100 comprises framework structure and the silicon embedded on framework structure Oxygen material;
- the skeleton structure includes a lithium silicate skeleton (i.e. lithium silicate 120) inside the active material and a magnesium silicate skeleton (i.e. water-insoluble silicate 140) on the surface of the active material, a magnesium silicate skeleton (i.e. water-insoluble Lithium silicate 140) is connected to the lithium silicate skeleton.
- the lithium silicate skeleton (i.e. lithium silicate 120) in this embodiment is Li 2 Si 2 O 5 , Li 2 SiO 3 , Li 4 SiO 4 , and the surface layer of the active material (i.e. water-insoluble silicate 140) is Li 2 MgSiO 4 .
- the negative electrode material prepared in this example has an average particle size (D 50 ) of 5.0 ⁇ m, a tap density of 0.98 g/cm 3 , a specific surface area of 2.54 m 2 /g, and a mass percentage content of lithium in the negative electrode material of 9.5 wt. %, the thickness of the carbon layer is 183nm.
- the structural representation of the negative electrode material prepared in the present embodiment is with reference to Fig. 3, and it comprises active material 100 and the carbon layer (that is cladding layer 200) that is formed on the surface of active material, and active material 100 comprises framework structure and the silicon embedded on framework structure Oxygen material;
- the skeleton structure includes a lithium silicate skeleton (i.e. lithium silicate 120) inside the active material and a magnesium silicate skeleton (i.e. water-insoluble silicate 140) on the surface of the active material, a magnesium silicate skeleton (i.e. water-insoluble Lithium silicate 140) is connected to the lithium silicate skeleton.
- the lithium silicate skeleton i.e.
- lithium silicate 120) in this embodiment is Li 2 Si 2 O 5 , Li 2 SiO 3 , Li 4 SiO 4 , and the surface layer of the active material (i.e. water-insoluble silicate 140) is Mg 2 SiO 4.
- the negative electrode material prepared in this example has an average particle size (D 50 ) of 5.0 ⁇ m, a tap density of 0.98 g/cm 3 , a specific surface area of 2.54 m 2 /g, and a mass percentage content of lithium in the negative electrode material of 9.5 wt. %, the thickness of the carbon layer is 183nm.
- the XRD diffraction pattern of the negative electrode material prepared in this embodiment is shown in FIG. 6 .
- Step (1) is close to Example 1, except that lithium content is 11wt%;
- Step (2) is similar to Example 1, except that the pre-lithiated material is soaked in 12wt% acetic acid solution for 1.2h;
- Step (3) Add Al 2 O 3 (7.5g) and surface-etched pre-lithium silicon oxide (100g) into a ball mill. After ball milling for 10 hours, transfer to a graphite crucible and treat at 850°C under a protective atmosphere After 10 hours, the negative electrode material was obtained by crushing, sieving and classifying.
- the structural representation of the negative electrode material prepared in the present embodiment is with reference to Fig. 3, and it comprises active material 100 and the carbon layer (that is cladding layer 200) that is formed on the surface of active material, and active material 100 comprises framework structure and the silicon embedded on framework structure Oxygen material;
- the skeleton structure includes a lithium silicate skeleton (i.e. lithium silicate 120) inside the active material and a magnesium silicate skeleton (i.e. water-insoluble silicate 140) on the surface of the active material, a magnesium silicate skeleton (i.e. water-insoluble Lithium silicate 140) is connected to the lithium silicate skeleton.
- the lithium silicate skeleton i.e.
- lithium silicate 120) in this embodiment is Li 2 Si 2 O 5 , Li 2 SiO 3 , Li 4 SiO 4 , and the surface layer of the active material (i.e. water-insoluble silicate 140) is Al 2 SiO 5.
- the average particle size (D 50 ) of the negative electrode material prepared in this example is 5.0 ⁇ m, the tap density is 0.98 g/cm 3 , the specific surface area is 2.77 m 2 /g, and the mass percentage content of lithium in the negative electrode material is 9.6 wt %, the thickness of the carbon layer is 177nm.
- Step (1) is close to Example 1, except that lithium content is 11wt%;
- Step (2) is similar to Example 1, except that the pre-lithiated material is soaked in 1wt% nitric acid solution for 0.5h;
- Step (3) Add Na 2 CO 3 (8g) and pre-lithium silicon oxide (100g) after surface etching into a ball mill, after ball milling for 10h, transfer to a graphite crucible, and treat at 850°C for 10h under a protective atmosphere Afterwards, the negative electrode material is obtained by crushing, sieving and classifying.
- the structural representation of the negative electrode material prepared in the present embodiment is with reference to Fig. 3, and it comprises active material 100 and the carbon layer (that is cladding layer 200) that is formed on the surface of active material, and active material 100 comprises framework structure and the silicon embedded on framework structure Oxygen material;
- the skeleton structure includes a lithium silicate skeleton (i.e. lithium silicate 120) inside the active material and a magnesium silicate skeleton (i.e. water-insoluble silicate 140) on the surface of the active material, a magnesium silicate skeleton (i.e. water-insoluble Lithium silicate 140) is connected to the lithium silicate skeleton.
- the lithium silicate skeleton ie lithium silicate 120
- the active material surface layer ie water-insoluble silicate 140
- the average particle size (D 50 ) of the negative electrode material prepared in this example is 5.0 ⁇ m, the tap density is 1.00 g/cm 3 , the specific surface area is 2.79 m 2 /g, and the mass percentage content of lithium in the negative electrode material is 10.0 wt %, the thickness of the carbon layer is 193nm.
- Step (1) is similar to Example 1, except that the carbon-coated silicon-oxygen material is reacted with silicon-oxygen material SiO 0.75 /C with a silicon content of 65% to obtain a pre-lithiated carbon-coated silicon-oxygen material Li ⁇ SiO 0.75 //C, wherein the lithium content is 10wt%;
- the structural representation of the negative electrode material prepared in the present embodiment is with reference to Fig. 3, and it comprises active material 100 and the carbon layer (that is cladding layer 200) that is formed on the surface of active material, and active material 100 comprises framework structure and the silicon embedded on framework structure Oxygen material;
- the skeleton structure includes a lithium silicate skeleton (i.e. lithium silicate 120) inside the active material and a magnesium silicate skeleton (i.e. water-insoluble silicate 140) on the surface of the active material, a magnesium silicate skeleton (i.e. water-insoluble Lithium silicate 140) is connected to the lithium silicate skeleton.
- the lithium silicate skeleton i.e.
- lithium silicate 120) in this embodiment is Li 2 Si 2 O 5 , Li 2 SiO 3 , Li 4 SiO 4 , and the surface layer of the active material (i.e. water-insoluble silicate 140) is Mg 2 SiO 4 , MgSiO 3 , Li 2 MgSiO 4 .
- the negative electrode material prepared in this example has an average particle size (D 50 ) of 5.0 ⁇ m, a tap density of 1.1 g/cm 3 , a specific surface area of 2.47 m 2 /g, and a mass percent content of lithium in the negative electrode material of 9.5 wt. %, the thickness of the carbon layer is 187nm.
- the negative electrode material prepared in this embodiment includes a mixture of active material and magnesium oxide.
- the negative electrode material prepared in this example has an average particle size (D 50 ) of 5.0 ⁇ m, a tap density of 0.98 g/cm 3 , a specific surface area of 2.54 m 2 /g, and a mass percentage content of lithium in the negative electrode material of 9.5 wt. %, the thickness of the carbon layer is 183nm.
- the negative electrode material prepared in this embodiment includes a mixture of active material and magnesium oxide.
- the negative electrode material prepared in this example has an average particle size (D 50 ) of 5.0 ⁇ m, a tap density of 0.98 g/cm 3 , a specific surface area of 2.54 m 2 /g, and a mass percentage content of lithium in the negative electrode material of 9.5 wt. %, the thickness of the carbon layer is 183nm.
- Steps (1) to (2) are identical with embodiment 8;
- Step (3) is close to Example 8, except that the addition of magnesium oxide is 11g
- the negative electrode material prepared in this embodiment includes a mixture of active material and magnesium oxide.
- the average particle size (D 50 ) of the negative electrode material prepared in this example is 5.0 ⁇ m, the tap density is 0.89 g/cm 3 , the specific surface area is 3.2 m 2 /g, and the mass percentage content of lithium in the negative electrode material is 9.2 wt %, the thickness of the carbon layer is 187nm.
- the preparation method is similar to that of Example 1, except that in step (1), the silicon-oxygen material SiO is reacted with metal lithium to obtain a pre-lithiated carbon-coated silicon-oxygen material Li-SiO;
- the average particle size (D 50 ) of the negative electrode material is 5.0 ⁇ m, the tap density is 0.98 g/cm 3 , the specific surface area is 3.01 m 2 /g, the mass percentage content of lithium in the negative electrode material is 10 wt%, and there is no carbon layer.
- the preparation method is close to Example 1, except that in step (2), the immersion time in the citric acid solution is 30min;
- the average particle diameter (D 50 ) of the negative electrode material is 5.0 ⁇ m, the tap density is 0.98g/cm 3 , the specific surface area is 2.74m 2 /g, the mass percentage content of lithium in the negative electrode material is 9.5wt%, the carbon layer The thickness is 189nm.
- Pre-lithiated carbon-coated silicon-oxygen material SiO-Li/C is used as the negative electrode material, with an average particle size (D 50 ) of 5.14 ⁇ m, a tap density of 0.98 g/cm 3 , and a specific surface area of 3.24 m 2 /g.
- the carbon content was 5.0 wt%.
- MgCl 2 can form magnesium hydroxide colloids or precipitates in an alkaline environment, and evenly wrap around the periphery of the carbon-coated pre-lithium material SiO-Li/C powder.
- the MgO part may be mixed with SiO 2 reacts with other silicic acid skeletons to form magnesium-containing silicate, and other MgO will evenly distribute and wrap the entire inner core to form a MgO coating layer and the outermost carbon coating layer to form a multi-layer coated core. shell structure.
- the negative electrode material prepared in this comparative example has an average particle size (D 50 ) of 5.17 ⁇ m, a tap density of 0.98 g/cm 3 , a specific surface area of 3.40 m 2 /g, a porosity of 2.17 wt%, and a carbon content of 5.0 wt. %.
- the mass ratio is mixed evenly, coated on the copper foil current collector, and dried to obtain the negative electrode sheet for use.
- the button battery test was carried out on the obtained pole piece.
- the battery was assembled in an argon glove box, with a lithium metal sheet as the negative electrode, the electrolyte was 1mol/LLiPF6+EC+EMC, and the separator was a polyethylene/propylene composite microporous membrane.
- the electrochemical performance is carried out on the battery testing equipment, the battery capacity is set to the standard 480mAh/g, the charge and discharge voltage is 0.01 ⁇ 1.5V, the charge and discharge rate is 0.1C, the charge and discharge test is carried out, and the first reversible capacity and the first cycle charge capacity are obtained. and first cycle discharge capacity.
- the first coulombic efficiency the discharge capacity of the first cycle / the charge capacity of the first cycle.
- a Malvern Mastersizer 2000 laser particle size tester was used to test the particle size of the negative electrode material to obtain the average particle size.
- the negative electrode material sample is heated and burned by a high-frequency furnace under oxygen-enriched conditions to oxidize carbon into carbon dioxide. After the gas is processed, it enters the corresponding absorption cell to absorb the corresponding infrared radiation and convert it into a corresponding signal by the detector. This signal is sampled by the computer, and converted into a value proportional to the carbon dioxide concentration after linear correction, and then the value of the entire analysis process is accumulated. After the analysis, the accumulated value is divided by the weight value in the computer, and then multiplied by the correction coefficient , and subtract the blank to obtain the percentage of carbon in the sample. Sample testing was performed using a high-frequency infrared carbon-sulfur analyzer (model Shanghai Dekai HCS-140).
- the negative electrode material sample was soaked in deionized water (the ratio of material to water was 50wt%), stirred for 24 hours and left to stand until the material liquid was separated, and the supernatant was taken for ICP test to obtain the lithium content.
- the pH value is the slurry pH value.
- the gas production is to draw 4ml into the sealed syringe (10ml small range syringe) after the slurry mixing is completed, and observe the volume change value of the slurry gas volume in the syringe after 8 hours.
- the test method is: the method is similar to the above method (i), the difference is that when adding HNO3 , an additional 6mL HF is added, and 4mL HNO3 Mix with 6mL HF to react.
- the negative electrode materials provided by Examples 1 to 3 the silicon-oxygen material is embedded in the skeleton structure, and the skeleton of the water-insoluble silicate of the outer layer and the inner silicon Lithium acid skeleton connection is conducive to the electrochemical performance of active materials, rapid electron transfer and lithium deintercalation, which is conducive to reducing the internal resistance of the material and improving the lithium ion transfer capacity.
- the encapsulation of the silicon-oxygen material by the skeleton of the water-insoluble silicate located on the outer layer can effectively prevent the contact of water with the strong alkaline lithium silicate and inhibit the hydrolysis of lithium silicate, thereby effectively improving the gas production of the material and realizing the protection of the material. pH regulation. Lithium ions can conduct through the skeleton structure and the silicon-oxygen material on the surface of the active material, which improves the ionic conductivity of the material and is conducive to the exertion of the rate performance of the material. For the performance data comparison of some examples and comparative examples, please refer to Figure 4-6 .
- Example 1 the in-situ growth of water-insoluble silicate on the SiO 2 skeleton forms a stable heterojunction interface with lithium silicate, which improves the conductivity of the material to 40.21 S/cm.
- Example 3 magnesium powder is used, and redox reaction occurs on the surface to form MgO and SiO 2 , which further improves the capacity and first effect, while MgO and SiO 2 react to form water-insoluble silicate (magnesium silicate), which can insulate the slurry with strong alkali silicates.
- Mg reduces the SiO skeleton, the part of the silicon-oxygen material extending through the lithium silicate is destroyed, and a part of the surface of the material particle forms a tight water-insoluble silicate interface, so the powder conductivity of Example 3 decreases relatively. In Example 1, slightly reduced.
- the composite negative electrode material only contains three components of Si/lithium silicate/magnesium silicate, and through the combination of the three materials, combined with the lithium content in the eluate , it can be found that a small amount of magnesium silicate is concentrated on the surface of the composite negative electrode material particles, and the new silicate interface forms a heterojunction structure, so the powder conductivity is much higher than that of lithium silicate/silicon and magnesium silicate/silicon samples (0.1- 10S/cm), thus the heterojunction structure on the surface of the composite anode material particles can be found.
- Example 4 uses Al 2 O 3
- Example 5 uses Na 2 CO 3 to grow in situ on silicon oxide respectively to form a stable heterojunction interface between water-insoluble silicate and lithium silicate, which also makes the material The electrochemical performance has been improved to a certain extent.
- Example 6 By using the silicon oxide material with a silicon content of 65% and magnesium oxide, it is also possible to grow in situ on the silicon oxide to form a stable heterojunction interface with lithium silicate and obtain a high electrochemical performance anode materials.
- the conventional pre-lithium material in Comparative Example 1 the conductivity of the material powder is low, this is because the silicon-based material and lithium silicate itself are insulators or semiconductors, and their conductivity as a battery core material is poor, so it can be found from the powder conductivity characterization , its powder conductivity is 7.21S/cm, while the powder conductivity of conventional graphite anode materials is above 250S/cm. Even if the surface is coated with conductive carbon, its conductivity is also very different from that of graphite anode materials.
- a layer of magnesium oxide coating layer is coated on the surface of granular carbon by deposition method.
- the magnesium oxide coating layer is deposited on the outer layer of the conductive layer, and the magnesium oxide coating layer covers the conductive carbon layer, reducing the structure of the conductive carbon layer and The contact of the conductive agent, therefore, the conductivity of the powder decreased significantly (0.37S/cm).
- the rate capacity retention rates of the batteries made of this material at 0.5C, 1C, and 2C are respectively lower than those of Comparative Example 1 by more than 3%.
- Examples 1-6 of the present disclosure can effectively ensure the high-efficiency reaction between the silicon-oxygen material after the surface etching treatment and the compound containing M or A when the processing temperature is kept within the scope of the present disclosure, not only The pH control of the material is realized to avoid gas production, and at the same time, the conductivity and rate performance of the powder are effectively improved, indicating that a more stable heterojunction structure is formed.
- Example 7 because the treatment temperature was low, the lithium silicate on the surface and the SiO2 skeleton and magnesium oxide reacted slowly, causing gas production to occur, but the gas production was significantly lower than that of the comparative example, and the electrical conductivity of the powder was slightly lower than that of the comparative example. Improvement, the rate performance is lower than that of Example 1, indicating that a heterojunction structure has been formed.
- the cycle capacity retention rate of the battery is also related to the heterojunction structure in the negative electrode material.
- the 50-cycle capacity retention rate is above 90%, while In Comparative Example 1 showing two-stage differentiation, without a heterojunction structure, the 50-week capacity retention rate was nearly 10% lower, while in Comparative Example 2, the conductivity decreased due to the surface coating of magnesium oxide, and the capacity could not be exerted, which resulted in a low capacity retention rate of 10%. Chemical properties are reduced.
- the range of pm/p Li is within the scope of the present disclosure, which can further ensure the high mass-charge conductivity of the material, further effectively suppress the alkalinity of the material, and avoid the production of negative electrode materials during processing. gas, thereby further improving the first efficiency and cycle stability of the battery.
- the negative electrode material provided by the disclosure can improve processing performance, has excellent electrochemical cycle and expansion inhibition performance, can prolong the service life of lithium-ion batteries, and its preparation method is simple, low in cost, and easy to realize industrial production, so it has excellent industrial Practical performance.
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Abstract
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Claims (13)
- 一种负极材料,其特征在于,所述负极材料包括活性材料,所述活性材料包括贯穿所述活性材料的骨架结构及镶嵌于所述骨架结构上的硅氧材料;所述骨架结构包括位于所述活性材料内部的硅酸锂的骨架及位于所述活性材料表层的非水溶性硅酸盐的骨架,所述非水溶性硅酸盐的骨架与所述硅酸锂的骨架连接;其中,所述负极材料的XRD图谱中,所述硅酸锂的最强衍射特征峰的强度为I A,所述非水溶性硅酸盐的最强衍射特征峰的强度为I B,且0.03≤I B/I A≤0.2。
- 一种负极材料,其特征在于,所述负极材料包括活性材料;所述活性材料包括硅酸锂、非水溶性硅酸盐和硅氧材料;其中,所述非水溶性硅酸盐包覆于所述硅酸锂的表面;所述硅酸锂和/或所述非水溶性硅酸盐中含有所述硅氧材料,其中,所述负极材料的XRD图谱中,所述硅酸锂的最强衍射特征峰的强度为I A,所述非水溶性硅酸盐的最强衍射特征峰的强度为I B,且0.03≤I B/I A≤0.2。
- 根据权利要求1或2所述的负极材料,其特征在于,其满足以下条件a~g的至少一者:a.所述硅氧材料为SiO n,其中,0.5≤n≤1.5;b.所述硅酸锂包括Li 2SiO 3、Li 2Si 2O 5、Li 4SiO 4、Li 2Si 3O 7、Li 8SiO 6、Li 6Si 2O 7、Li 4Si 2O 7、Li 2Si 4O 7和LiSiO 3中的至少一种;c.所述非水溶性硅酸盐包括zA 2O·MO y·xSiO 2,其中,M包括Mg、Al、Ca、Ge、Cr、V、Ti、Sc、Co、Ni、Cu、Sr、Zn、Zr、Fe和Mn中的至少一种,A包括Li、Na、K中的至少一种,0.2≤x≤10.0,1.0≤y≤3.0,0≤z≤5.0;d.所述非水溶性硅酸盐还包括A 2O·nSiO 2,其中,其中A包括Li、Na、K中的至少一种,1≤n≤10;e.所述非水溶性硅酸盐的功函数范围为2.5eV≤η≤7.0eV;f.所述非水溶性硅酸盐位于所述活性材料表面20nm~50nm的深度区域内;g.所述非水溶性硅酸盐中的Li元素的质量含量为W 1%,所述硅酸锂中的Li元素含量为W 2%,W 2>W 1≥0。
- 根据权利要求1-3中任一项所述的负极材料,其特征在于,其满足以下条件a~j的至少一者:a.所述负极材料还包括存在于所述活性材料表面的碳层;b.所述碳层的平均厚度为30nm~500nm;c.所述负极材料的振实密度为0.6g/cm 3~1.20g/cm 3;d.所述负极材料的比表面积为1.0m 2/g~12.0m 2/g;e.所述负极材料的平均粒径为3.0μm~12.0μm;f.所述负极材料中的碳的质量百分比含量为1.5wt%~10.0wt%;g.所述负极材料中的锂的质量百分比含量为3wt%~15wt%;h.所述负极材料的pH为8.5~12.0;i.所述负极材料的XRD图谱中,所述硅酸锂的最强衍射特征峰的强度为I A,所述非水溶性硅酸盐的最强衍射特征峰的强度为I B,且0.12≤I B/I A≤0.18;j.所述负极材料的非水溶性硅酸盐中锂元素含量为pm,所述负极材料的总锂元素含量为p Li,其中0.01≤pm/p Li≤0.6。
- 一种负极材料的制备方法,其特征在于,包括以下步骤:将预锂化的硅氧材料进行表面刻蚀处理;将表面刻蚀处理后的硅氧材料与含金属M和/或金属A的物质混合,在保护气氛下进行固相热反应,得到所述负极材料。
- 根据权利要求5所述的方法,其特征在于,其满足以下条件i~iv的至少一者:(i)所述含金属A的物质包括:金属A单质、金属A的碳酸盐、金属A的氧化物、金属A氢氧化物中的至少一种,其中,A包括Li、Na、K中的至少一种;(ii)所述含金属M的物质包括金属M单质、金属M的碳酸盐、金属M的氧化物、金属M的氢氧化物中的至少一种,其中,M包括Mg、Al、Ca、Ge、Cr、Pb、Sr、Zn、Zr、Fe和Mn中的至少一种;(iii)所述表面刻蚀处理后的硅氧材料与所述含金属M和/或金属A的物质的质量比为1:(0.01~0.1);(iv)所述表面刻蚀处理后的硅氧材料与所述含金属M和/或金属A的物质的质量比为1:(0.075~0.1)。
- 一种负极材料的制备方法,其特征在于,包括以下步骤:将预锂化的硅氧材料进行表面刻蚀处理;将表面刻蚀处理后的硅氧材料与含金属M的化合物混合,在保护气氛下进行固相热反应,得到所述负极材料。
- 根据权利要求7所述的方法,其特征在于,其满足以下条件a~d的至少一者:a.所述含金属M的化合物包括金属M的碳酸盐、金属M的氧化物、金属M的氢氧化物中的至少一种,其中,M包括Mg、Al、Ca、Ge、Cr、Pb、Sr、Zn、Zr、Fe和Mn中的至少一种;b.所述表面刻蚀处理后的硅氧材料与所述含金属M的化合物的质量比为1:(0.01~0.1);c.所述表面刻蚀处理后的硅氧材料与所述含金属M的化合物的质量比为1:(0.075~0.1);d.所述含金属M的化合物为金属M的氧化物。
- 根据权利要求5-8中任一项所述的方法,其特征在于,其满足以下条件a~f的至少一者:a.所述混合方式包括机械搅拌、超声分散及研磨分散中的至少一种;b.所述混合方式为球磨混合,所述球磨时间为3h~24h;c.所述保护气氛的气体包括氮气、氦气、氖气、氩气、氪气和氙气中的至少一种;d.所述固相热反应的温度为600℃~1200℃;e.所述固相热反应的时间为3h~12h;f.所述固相热反应的升温速率为1℃/min~5℃/min。
- 根据权利要求5-9任一项所述的方法,其特征在于,其满足以下条件a~k的至少一者:a.所述预锂化的硅氧材料为预锂化的碳包覆硅氧材料;b.所述预锂化的碳包覆硅氧材料由碳包覆硅氧材料与锂源反应得到;c.所述硅氧材料为SiO n,其中,0.5≤n≤1.5;d.所述硅氧材料的平均粒径(D 50)为2.0μm~15.0μm;e.所述碳包覆硅氧材料表面的碳层的厚度为30nm~500nm;f.所述锂源包括锂单质或含有锂的化合物中的至少一种;g.所述锂源包括氢化锂、烷基锂、金属锂、氢化铝锂、氨基锂和硼氢化锂中的至少一种;h.所述碳包覆硅氧材料与所述锂源的反应温度为150℃~300℃;i.所述碳包覆硅氧材料与所述锂源的反应时间为2.0h~6.0h;j.所述碳包覆硅氧材料与所述锂源的质量比为1:(0.01~0.20);k.所述预锂化的碳包覆硅氧材料中的锂的质量百分比含量为3wt%~20wt%。
- 根据权利要求5-9任一项所述的方法,其特征在于,在将所述预锂化的硅氧材料进行表面刻蚀处理之前,所述方法还包括:将所述硅氧材料与锂源反应得到的预锂化的硅氧材料;或将碳包覆硅氧材料与锂源反应得到的预锂化的碳包覆硅氧材料。
- 根据权利要求5-9任一项所述的方法,其特征在于,其满足以下条件a~c的至少一者:a.所述表面刻蚀处理采用的酸溶液具有的特性为:在将所述预锂化的硅氧材料进行表面刻蚀处理时,保持所述表面刻蚀的反应体系pH<7;b.所述表面刻蚀处理采用的酸溶液包括盐酸、醋酸、硝酸、柠檬酸、草酸、硫酸、甲酸、苯酚、磷酸、磷酸氢化物、氢碘酸、氢溴酸、乙二胺四乙酸、羟基乙酸、葡萄糖酸、丁二酸中的至少一种;c.所述表面刻蚀处理的时间为0.5h~10.0h。
- 一种锂离子电池,其特征在于,所述锂离子电池包含权利要求1-4任一项所述的负极材料或根据权利要求5-12任一项所述的负极材料的制备方法制得的负极材料。
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