CN113410448A - Silicon monoxide composite negative electrode material of lithium ion battery and preparation method thereof - Google Patents
Silicon monoxide composite negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN113410448A CN113410448A CN202110713263.7A CN202110713263A CN113410448A CN 113410448 A CN113410448 A CN 113410448A CN 202110713263 A CN202110713263 A CN 202110713263A CN 113410448 A CN113410448 A CN 113410448A
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- China
- Prior art keywords
- negative electrode
- electrode material
- silicon monoxide
- lithium ion
- composite negative
- Prior art date
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 145
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 59
- 238000002156 mixing Methods 0.000 claims description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000005530 etching Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000011265 semifinished product Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
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- 238000010438 heat treatment Methods 0.000 claims description 14
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- 239000002184 metal Substances 0.000 claims description 14
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- 238000001914 filtration Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
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- 229910020489 SiO3 Inorganic materials 0.000 claims description 9
- 229910052839 forsterite Inorganic materials 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 abstract description 13
- 239000010406 cathode material Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 235000002639 sodium chloride Nutrition 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 11
- 230000006872 improvement Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001103 potassium chloride Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000011294 coal tar pitch Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 238000006722 reduction reaction Methods 0.000 description 4
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of battery cathode materials, in particular to a lithium ion battery silicon monoxide composite cathode material which comprises an outer shell layer and an inner shell layer; the outer shell layer is an amorphous carbon layer; the inner shell layer is a porous structure silicate layer. The fused salt magnesium thermal reaction method is used for preparing the silicon oxide composite negative electrode material, so that a reaction system is converted from solid-solid reaction into solid-liquid reaction or liquid-like reaction, the reaction efficiency and the reaction uniformity are obviously improved, the material has high first effect on the premise of ensuring higher capacity, the prepared silicon oxide negative electrode material with the double-shell structure obviously improves the material cycle performance, the overall performance of the material is excellent, and meanwhile, the large-scale mass production can be realized. The invention also provides a preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery, which obviously improves the first-week efficiency of the material, has no special equipment requirement and no special environmental requirement, has simple integral process and is very beneficial to large-scale commercialization.
Description
Technical Field
The invention relates to the field of battery cathode materials, in particular to a silicon monoxide composite cathode material of a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries have become a hot spot in current world research due to the advantages of large specific capacity, long service life, high safety, convenience in carrying and the like, and are widely applied to various electronic devices, electric automobiles and portable energy storage devices. The silicon-based material as a novel lithium ion secondary battery cathode material has higher specific capacity compared with graphite, but has quite obvious defects, large volume expansion, poor rate capability and low first charge-discharge efficiency, and the active material is easy to pulverize and fall off during the charge-discharge process to seriously influence the service life of the lithium ion secondary battery cathode material. Compared with nano silicon, the volume expansion of the silicon oxide anode material serving as a silicon-based material is relatively small, and the silicon oxide anode material has great advantages in later production improvement.
The silicon protoxide material still has higher theoretical specific capacity (more than 2000mAh/g) compared with graphite, but the defect is very obvious, the cycle performance and the rate performance of the silicon protoxide material are much poorer than those of the graphite, and in addition, the first-cycle efficiency of the silicon protoxide material is far lower than that of the graphite material, mainly because lithium ions can react with a silicon oxygen material to generate Li2O and Li2SiO4 in the first charging and discharging process of the silicon protoxide material, and more active lithium is consumed to cause the first-cycle efficiency to be low. Therefore, the research of the silicon oxide negative electrode material by researchers at present mainly focuses on the aspects of the cycle performance, rate performance improvement and first efficiency improvement of the material, which is also a significant difficulty in the research of the silicon oxide negative electrode material at present.
At present, most researchers adopt a method of simply coating carbon on the surface of silicon oxide to improve the cycle performance of a silicon oxide negative electrode material, and adopt a method of coating carbon on the surface to modify the performance of the silicon oxide negative electrode material, but the improvement is limited, the cycle performance of the material can be improved only to a certain extent, and the improvement effect on the first cycle efficiency and the rate capability of the material is poor.
Some researchers use a metal substance reduction method to improve the performance of the material, and all adopt metal substances to carry out reduction reaction on the material, so that the first-week efficiency of the material is improved, but because an effective method is not adopted to control heat release and reaction uniformity in the reaction process, the actual reaction efficiency is extremely uneven and the reaction efficiency is low, the prepared material does not reach a higher level, and the cycle performance and the rate performance are obviously reduced; in addition, researchers adopt a pre-lithium method to improve material performance, all adopt the pre-lithium method to modify materials, and compared with other methods, the pre-lithium method can effectively and greatly improve the first-cycle efficiency of the materials, but the pre-lithium method has obvious defects of high pre-lithium agent activity, harsh conditions required by early preparation, complex experimental preparation process, large difficulty in mass production and serious shortage of single-batch preparation quantity.
Aiming at the current research situation and research progress of the current silicon monoxide negative electrode material, an effective method is urgently needed to enable the cycle performance of the prepared material to be greatly improved, the first-cycle efficiency and the rate capability of the prepared material are greatly improved, and the development requirement of the current silicon monoxide negative electrode material is met.
Disclosure of Invention
In order to solve the technical problems, the invention provides the silicon monoxide composite negative electrode material of the lithium ion battery, which effectively relieves the cyclic expansion performance of the material, and the inner silicate structure contains various cavities, so that the problem of lithium ion migration rate is greatly improved, and the multiplying power of the material is also obviously improved.
The invention also provides a preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery, which obviously improves the first-week efficiency of the material, has no special equipment requirement and no special environmental requirement, has simple integral process and is very beneficial to large-scale commercialization.
The invention adopts the following technical scheme:
a lithium ion battery silicon monoxide composite negative electrode material comprises an outer shell layer and an inner shell layer; the outer shell layer is an amorphous carbon layer; the inner shell layer is a porous structure silicate layer.
In a further improvement of the above solution, the porous structure silicate layer comprises Mg2SiO4And Mg2SiO3The porous channel structure of the porous structure silicate layer is formed by acid etching.
A preparation method of a silicon monoxide composite negative electrode material of a lithium ion battery comprises the following steps:
(1) preparing a raw material of the silicon monoxide;
(2) uniformly mixing the silicon monoxide prepared in the step (1) with metal magnesium powder and molten salt to obtain a precursor A;
(3) carrying out high-temperature treatment on the precursor A in the step (2) under a protective atmosphere, and carrying out roasting reaction, cooling, acid washing and etching to obtain a semi-finished product B; the acid pickling etching mainly comprises the working procedures of mixing, stirring, filtering and drying a roasted cooling material and an acid solution;
(4) and (3) blending the semi-finished product B and the carbon coating material in the step (3), or coating the semi-finished product B by adopting a gas phase, roasting and carbonizing the semi-finished product B in a protective atmosphere, cooling the semi-finished product B to obtain a silicon oxide/carbon coated composite negative electrode material, and crushing, crushing and screening the silicon oxide/carbon coated composite negative electrode material to obtain the silicon oxide composite negative electrode material of the lithium ion battery.
The technical scheme is further improved in that in the step (1), the raw material of the silicon oxide is silicon oxide powder with the particle size median diameter D50 of 1-50 μm, the particle size and the shape are controlled by any one of a ball mill, a crusher and a pulverizer, and the qualified raw material of the silicon oxide is prepared by sieving and demagnetizing.
The technical scheme is further improved in that in the step (2), the metal magnesium powder is in a solid powder state, the particle size D50 is 0.1-500 mu m, and the purity of the metal magnesium powder is more than or equal to 95.0%; the molar ratio of the silicon monoxide to the metal magnesium powder is 1: 0.01-1: 1.
In the step (2), the molten salt is in a solid particle or powder form, and the particle size median diameter (D50) of the molten salt is 0.5-1000 μm; the addition mass ratio of the silicon monoxide to the molten salt is 1: 0.1-1: 20.
The technical scheme is further improved in that in the step (3), the heating rate is 0.1-20 ℃/min, the temperature is 200-1000 ℃, and the heat preservation time is 0.5-24 h.
The technical scheme is further improved in that in the step (3), the acid pickling etching comprises normal temperature etching and heating etching, and the concentration of the acid liquor is 0.1-10.0 mol/L.
The technical scheme is further improved in that in the step (3), the mass ratio of the roasting cooling material to the acid liquor is 1: 0.5-1: 15.
The technical scheme is further improved in that in the step (4), the roasting carbonization treatment temperature is 500-1100 ℃, and the heat preservation time is 2-8 h.
The invention has the beneficial effects that:
1. the fused salt magnesium thermal method can obviously control the silicon crystal grain enlargement in the material reduction process, simultaneously greatly improves the reaction efficiency and reaction uniformity, and greatly improves the cycle performance of the material along with the improvement of the reaction process;
2. mg with porous structure generated in preparation process2SiO3，Mg2SiO4The structural layer has a good effect on inhibiting the expansion of the material, and the porous structure can effectively improve the ionic conductivity of the material, improve the rate capability of the material and have a remarkable improvement effect on the cycle performance of the material;
3. amorphous carbon structure and porous Mg2SiO3，Mg2SiO4The structure layer has a double-layer coating structure, and has better effect on active substances in the charge and discharge processesThe protective effect of the carbon structure can effectively avoid the loss of a large amount of active substances caused by the contact of the carbon structure and the electrolyte, and the carbon structure can improve the conductivity of the material, reduce the specific surface and obviously improve the cycle performance of the material.
4. According to the invention, the fused salt magnesium thermal reaction method is used for preparing the silicon oxide composite negative electrode material, so that a reaction system is converted from solid-solid reaction into solid-liquid reaction or liquid-like reaction, the reaction efficiency and the reaction uniformity are obviously improved, the material has high first effect on the premise of ensuring higher capacity, the prepared silicon oxide negative electrode material with the double-shell structure obviously improves the material cycle performance, the material has excellent overall performance, and meanwhile, the large-scale mass production can be realized.
Drawings
FIG. 1 is a schematic structural diagram of a silicon monoxide composite negative electrode material of a lithium ion battery of the present invention;
FIG. 2 is a schematic structural diagram of a material tested by an X-ray diffractometer X' Pert Pro, PANALYTICAL test for a silicon oxide composite negative electrode material of a lithium ion battery of the invention;
FIG. 3 is an X-ray diffraction pattern of a silicon monoxide composite negative electrode material of a lithium ion battery of example 1 of the present invention.
Detailed Description
For the convenience of understanding the present invention, the following examples are listed. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
A lithium ion battery silicon monoxide composite negative electrode material comprises an outer shell layer and an inner shell layer; the outer shell layer is an amorphous carbon layer; the inner shell layer is a porous structure silicate layer.
The porous structure silicate layer includes Mg2SiO4And Mg2SiO3The porous channel structure of the porous structure silicate layer is formed by acid etching.
A preparation method of a silicon monoxide composite negative electrode material of a lithium ion battery comprises the following steps:
(1) preparing a raw material of the silicon monoxide;
(2) uniformly mixing the silicon monoxide prepared in the step (1) with metal magnesium powder and molten salt to obtain a precursor A;
(3) carrying out high-temperature treatment on the precursor A in the step (2) under a protective atmosphere, and carrying out roasting reaction, cooling, acid washing and etching to obtain a semi-finished product B; the pickling etching mainly comprises the working procedures of mixing, stirring, filtering and drying the roasted cooling material and the acid liquor, and the pickling etching mainly comprises the working procedures of mixing, stirring, filtering and drying the material and the acid liquor;
(4) and (3) blending the semi-finished product B and the carbon coating material in the step (3), or coating the semi-finished product B by adopting a gas phase, roasting and carbonizing the semi-finished product B in a protective atmosphere, cooling the semi-finished product B to obtain a silicon oxide/carbon coated composite negative electrode material, and crushing, crushing and screening the silicon oxide/carbon coated composite negative electrode material to obtain the silicon oxide composite negative electrode material of the lithium ion battery.
Preferably, the silica raw material in the step (1) is silica powder with a median particle size D50 of 1-50 μm, and the qualified silica raw material is prepared by controlling particle size and shape mainly through a ball mill, a crusher, a pulverizer and other equipment, sieving, and removing magnetism.
Preferably, the mixing mode in the step (2) can adopt VC mixing equipment, V-shaped mixing equipment, mechanical stirring and mixing and the like, the mixing rotating speed is 100-2000 rpm, and the mixing time is 0.2-5.0 h.
Preferably, the magnesium metal powder in the step (2) is in a solid powder state, and the particle size D50 is 0.1-500 μm; the purity of the metal magnesium powder is more than or equal to 95.0 percent.
Preferably, the molar ratio of the silicon monoxide to the metal magnesium powder in the step (2) is 1: 0.01-1: 1, and more preferably 1: 0.08-1: 0.8, when the amount of the added active magnesium powder is too large, a large amount of impurities which cannot be removed are easily generated in the reaction process, and the grain size of the active material is obviously increased; when the amount of the added magnesium powder is too small, the reaction is insufficient, so that the oxygen content of the active material is too high, and the performance of the material is not obviously improved.
Preferably, the molten salt in step (2) is in the form of solid particles or powder.
Preferably, the particle size median diameter (D50) of the molten salt in the step (2) is 0.5-1000 μm, more preferably 10-500 μm, the small particle size of the molten salt is beneficial to uniform mixing, and the molten salt is easier to melt in the reaction process.
Preferably, the addition mass ratio of the silicon monoxide to the molten salt in the step (2) is 1: 0.1-1: 20, and more preferably 1: 0.5-1: 10.
A large amount of reaction heat is released in the magnesium thermal reaction process, the temperature of a reaction system can be increased rapidly, the crystal grains of the material are increased rapidly and can not be controlled, after the molten salt is introduced, the molten salt can absorb a large amount of reaction heat, meanwhile, the contact surface of magnesium powder and the material can be reduced due to the existence of the molten salt, the heat release of the simultaneous reaction is reduced, the temperature of the system is controlled to be increased rapidly, and the effect of controlling the crystal grains of the material is achieved.
Preferably, the molten salt in step (2) is one or more of calcium chloride, lithium chloride, magnesium chloride, aluminum chloride, iron dichloride, cobalt chloride, barium chloride, ferric chloride, potassium chloride, sodium chloride, nickel chloride, potassium bromide, cesium bromide, sodium bromide, rubidium bromide, potassium carbonate, potassium sulfate, lithium carbonate, sodium sulfate, lithium hydroxide, magnesium carbonate, magnesium sulfate, magnesium bromide, calcium carbonate, titanium chloride, chromium chloride, manganese chloride, copper chloride, zinc chloride, tin chloride and the like, and particularly preferably one or more of calcium chloride, lithium chloride, aluminum chloride, magnesium chloride, iron dichloride, ferric trichloride, potassium chloride, sodium chloride, potassium sulfate and potassium carbonate;
preferably, the protective atmosphere in step (3) is an inert gas, a reducing gas, or the like; the inert gas is one or a mixture of more of nitrogen, argon, helium, neon, krypton and xenon; the reducing gas is hydrogen, and particularly preferably one or more mixed gases of nitrogen, argon and hydrogen.
Preferably, the temperature rise rate in the step (3) is 0.1-20 ℃/min, the temperature is 200-1000 ℃, and the heat preservation time is 0.5-24 h.
Preferably, the roasting device in the step (3) is a box furnace, a rotary furnace, a roller kiln and the like; and the cooling is to naturally cool to room temperature under a protective atmosphere.
Preferably, the acid etching in the step (3) includes normal temperature etching and heating etching, the concentration of the acid solution is 0.1-10.0 mol/L, the heating etching is further preferred, and the etching temperature is 40-120 ℃.
The heating etching can obviously improve the acid liquid etching efficiency and the etching depth, can partially remove the residual redundant magnesium thermal by-products on the surface of the silicon oxide, improves the initial capacity of the material, and simultaneously generates more complex cavities on the silicate layer on the surface of the silicon oxide, thereby being beneficial to improving the ion transmission performance of the material.
Preferably, the acid solution in step (3) is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, carbonic acid and oxalic acid, and more preferably one or more of hydrochloric acid, sulfuric acid and acetic acid.
Preferably, the mass ratio of the roasting cooling material and the acid liquor in the step (3) is 1: 0.5-1: 15, and more preferably 1: 0.8-1: 8.
Preferably, the blending stirring speed in the step (3) is 100-2000 rpm, the stirring time is 0.5-24 h, and the stirring mode is mechanical stirring or magnetic stirring.
Preferably, the filtration in the acid pickling etching in the step (2) adopts a filter press, a centrifuge and vacuum filtration, more preferably adopts a filter press and a centrifuge, and the drying adopts an air blast drying oven or vacuum drying.
Preferably, the blending in step (4) is the same as the blending method in step (1).
Preferably, the carbon-coated material in the step (4) is one or more of coal tar pitch, petroleum pitch, starch, polyvinyl chloride, glucose, epoxy resin, polystyrene, phenolic resin, urea-formaldehyde resin, polyurethane, polythiophene, polyhydric alcohols, and the like, and is obtained by high-temperature treatment, more preferably one or more of coal tar pitch, petroleum pitch, starch, and glucose, and the like are powdery, and have a particle size of 10 to 1000 μm, and more preferably 100 to 500 μm; the addition mass ratio of the silicon monoxide to the carbon coating material is 1: 0.05-1: 1, more preferably 1: 0.1-1: 0.8, and particularly preferably 1: 0.2-1: 0.5.
Preferably, the reaction gas in the gas-phase coating in the step (4) is one or more of methane, ethane, propane, ethylene, acetylene, and the like, the gas flow rate is 1L/min-8L/min, and the aeration reaction time is 0.5-2 h.
Preferably, the temperature of the roasting carbonization treatment in the step (4) is 500-1100 ℃, and the cooling time is 2-8 h and is the same as that in the step (2).
And (3) crushing, crushing and screening the low-oxygen-value silicon oxide/carbon-coated composite negative electrode material in the step (3), wherein the particle size median diameter (D50) of the finally obtained silicon oxide composite negative electrode material of the lithium ion battery is 0.1-100 mu m.
Example 1
Silicon oxide with the median particle size (D50) of 0.5-2.5 mu m, magnesium metal powder with the median particle size (D50) of 5-30 mu m and CaCl with the particle size of 50-200 mu m2-AlCl3Carrying out VC mixing operation on the mixed molten salt at the mixing speed of 900rpm for 2h, wherein the adding molar ratio of the silicon monoxide to the magnesium metal powder material is 1:0.8, the adding mass ratio of the silicon monoxide to the mixed molten salt is 1:3, and the mixed molten salt CaCl2-AlCl3The mass ratio of the two is 6: 4. And (3) roasting the mixed material in a box type furnace under the protection of nitrogen atmosphere, wherein the roasting temperature is 500 ℃, the heating rate is 3 ℃/min, the heat preservation is carried out for 2h, and the material is taken out after being cooled completely. Adding the obtained material into 2mol/L hydrochloric acid, mixing and stirring, wherein the mass ratio of the obtained material to the hydrochloric acid is 1:3, the stirring rotation speed is 1500rpm, the stirring time is 5 hours, filtering is carried out by adopting a filter press after acid washing is finished, a blast air box is used for drying, the dried material and petroleum asphalt with the particle size median diameter (D50) of 100-500 mu m are blended, the blending mass ratio is 1:0.2, the mixed material is placed into a box type furnace for roasting, the nitrogen atmosphere is protected, the roasting temperature is 800 ℃, the heating rate is 2 ℃/min, the temperature is kept for 3 hours, the low-oxygen-value silicon oxide/carbon-coated composite negative electrode material is obtained, and the material is crushed, crushed and sieved, so that the particle size median particle diameter (D50) of the material is 0.1-100 mu m, namely the finished product of the silicon oxide composite negative electrode material for the lithium ion battery is obtained.
Example 2
Silica having a median particle diameter (D50) of 4 to 8 μmMagnesium metal powder having a particle diameter (D50) of 80 to 120 μm, MgCl of 50 to 200 μm2VC mixing is carried out on the-KCl mixed molten salt, the mixing speed is 800rpm, the mixing time is 2 hours, the adding molar ratio of the silicon monoxide to the magnesium metal powder material is 1:0.6, the adding mass ratio of the silicon monoxide to the mixed molten salt is 1:8, and the mixed molten salt is MgCl2The mass ratio between-KCl is 2: 8. And (3) placing the mixed materials into a box-type furnace for roasting, under the protection of argon atmosphere, keeping the roasting temperature at 750 ℃, keeping the temperature rise rate at 10 ℃/min, keeping the temperature for 8h, and taking out the materials after cooling completely. Adding the obtained material into 3mol/L hydrochloric acid, mixing and stirring, wherein the mass ratio of the obtained material to the hydrochloric acid is 1:6, the stirring rotation speed is 1500rpm, the stirring time is 5 hours, filtering is carried out by adopting a filter press after acid washing is finished, a blast air box is used for drying, the dried material and coal tar pitch with the particle size median diameter (D50) of 100-500 mu m are mixed, the mixing mass ratio is 1:0.2, the mixed material is placed into a box furnace for roasting, the atmosphere of argon is protected, the roasting temperature is 900 ℃, the heating rate is 2 ℃/min, the temperature is kept for 5 hours, the low-oxygen-value silicon oxide/carbon-coated composite negative electrode material is obtained, and the material is crushed, crushed and sieved, so that the particle size median particle diameter (D50) of the material is 0.1-100 mu m, namely the finished product of the silicon oxide composite negative electrode material for the lithium ion battery.
Example 3
Silicon oxide with the median particle size (D50) of 2.5-5 mu m, magnesium metal powder with the median particle size (D50) of 30-80 mu m and CaCl with the median particle size of 50-200 mu m2VC mixing operation is carried out on LiCl mixed molten salt, the mixing rotation speed is 1000rpm, the mixing time is 1h, the adding molar ratio of the silicon monoxide to the magnesium metal powder material is 1:0.4, the adding mass ratio of the silicon monoxide to the mixed molten salt is 1:5, and CaCl is mixed molten salt2The mass ratio between-LiCl was 3.5: 6.5. And (3) placing the mixed materials into a box-type furnace for roasting, under the protection of argon atmosphere, keeping the roasting temperature at 500 ℃, keeping the temperature rise rate at 5 ℃/min, keeping the temperature for 2h, and taking out the materials after cooling completely. Adding the obtained material into 3mol/L hydrochloric acid, mixing and stirring, wherein the mass ratio of the obtained material to the hydrochloric acid is 1:5, the stirring rotation speed is 1500rpm, the stirring time is 5 hours, filtering is carried out by adopting a filter press after the acid cleaning is finished, drying is carried out by using a blast air box, and the dried material and the particle size median diameter are mixed(D50) Blending 100-500 mu m coal tar pitch, wherein the blending mass ratio is 1:0.2, placing the mixed material into a box furnace for roasting, protecting in an argon atmosphere, roasting at the temperature of 1100 ℃, raising the temperature at the rate of 5 ℃/min, preserving heat for 5h, taking out the material after cooling completely to obtain a low-oxygen-value silicon oxide/carbon-coated composite negative electrode material, crushing and screening the material to obtain the material with the particle size median particle diameter (D50) of 0.1-100 mu m, namely the finished product of the silicon oxide composite negative electrode material for the lithium ion battery.
Example 4
Silica having a median particle size (D50) of 0.5 to 2.5 μm, magnesium metal powder having a median particle size (D50) of 5 to 30 μm, and MgCl having a median particle size of 50 to 200 μm2VC mixing is carried out on the-KCl mixed molten salt, the mixing speed is 800rpm, the mixing time is 2 hours, the adding molar ratio of the silicon monoxide to the magnesium metal powder material is 1:0.4, the adding mass ratio of the silicon monoxide to the mixed molten salt is 1:3, and the mixed molten salt is MgCl2The mass ratio between-KCl is 6: 4. And (3) placing the mixed materials into a box-type furnace for roasting, under the protection of nitrogen atmosphere, keeping the roasting temperature at 600 ℃, keeping the temperature rise rate at 3 ℃/min, keeping the temperature for 2h, and taking out the materials after cooling completely. Adding the obtained material into 2mol/L hydrochloric acid, mixing and stirring, wherein the mass ratio of the obtained material to the hydrochloric acid is 1:3, the stirring rotation speed is 1500rpm, the stirring time is 5 hours, filtering is carried out by adopting a filter press after acid washing is finished, a blast bellows is used for drying, the dried material is placed into a rotary furnace for roasting, the argon atmosphere is protected, the roasting temperature is 700 ℃, the heating rate is 7 ℃/min, when the temperature reaches 700 ℃, methane gas is started to be introduced, the flow is controlled to be 3L/min, the reaction time is 1 hour, the material is completely taken out after cooling, the low-oxygen-value silicon oxide/carbon-coated composite negative electrode material is obtained, and the material is crushed, crushed and screened to finally obtain the material with the particle size median particle size (D50) of 0.1-100 mu m, namely the finished product of the silicon oxide composite negative electrode material for the lithium ion battery.
Example 5
Silicon oxide with the median particle size (D50) of 2.5-5 mu m, magnesium metal powder with the median particle size (D50) of 30-80 mu m and CaCl with the median particle size of 50-200 mu m2VC mixing is carried out on KCl mixed molten salt, the mixing speed is 800rpm, and the mixing time is2h, wherein the adding molar ratio of the silicon monoxide to the magnesium metal powder material is 1:0.4, the adding mass ratio of the silicon monoxide to the mixed molten salt is 1:5, and the mixed molten salt CaCl2The mass ratio between-KCl is 2.6: 7.4. And (3) placing the mixed materials into a box-type furnace for roasting, under the protection of argon atmosphere, keeping the roasting temperature at 750 ℃, keeping the temperature rise rate at 5 ℃/min, keeping the temperature for 2h, and taking out the materials after cooling completely. Adding the obtained material into 3mol/L hydrochloric acid, mixing and stirring, wherein the mass ratio of the obtained material to the hydrochloric acid is 1:5, the stirring rotation speed is 1500rpm, the stirring time is 5 hours, filtering is carried out by adopting a filter press after acid washing is finished, a blast air box is used for drying, the dried material and starch with the particle size median diameter (D50) of 100-500 mu m are mixed, the mixing mass ratio is 1:0.2, the mixed material is placed into a box type furnace for roasting, the atmosphere protection of argon is carried out, the roasting temperature is 800 ℃, the heating rate is 5 ℃/min, the heat preservation is 3 hours, the material is completely taken out after cooling, the low-oxygen-value silicon oxide/carbon-coated composite negative electrode material is obtained, and the material is crushed, crushed and sieved, and the particle size median particle diameter (D50) of the material is 0.1-100 mu m, namely the finished product silicon oxide composite negative electrode material for the lithium ion battery is obtained.
Comparative example 1
Performing VC mixing operation on the magnesium metal powder with the particle size median diameter (D50) of 0.5-2.5 microns and the particle size median diameter (D50) of 5-30 microns, wherein the mixing rotation speed is 800rpm, and the mixing time is 2h, wherein the adding molar ratio of the silicon oxide to the magnesium metal powder material is 1: 0.2. And (3) placing the mixed materials into a box-type furnace for roasting, under the protection of nitrogen atmosphere, keeping the roasting temperature at 250 ℃, keeping the temperature rise rate at 3 ℃/min, keeping the temperature for 2h, and taking out the materials after cooling completely. Adding the obtained material into 2mol/L hydrochloric acid, mixing and stirring, wherein the mass ratio of the obtained material to the hydrochloric acid is 1:3, the stirring rotation speed is 1500rpm, the stirring time is 5 hours, filtering is carried out by adopting a filter press after acid washing is finished, a blast air bellow is used for drying, the dried material and coal tar pitch with the particle size median diameter (D50) of 100-500 mu m are mixed, the mixing mass ratio is 1:0.2, the mixed material is placed into a box furnace for roasting, the atmosphere of argon is protected, the roasting temperature is 800 ℃, the heating rate is 2 ℃/min, the temperature is kept for 3 hours, the material is completely taken out after cooling, the low-oxygen-value silicon oxide/carbon-coated composite negative electrode material is obtained, and the material is crushed, crushed and sieved, and the particle size median particle diameter (D50) of the material is 0.1-100 mu m, namely the finished product silicon oxide composite negative electrode material for the lithium ion battery is obtained.
Comparative example 2
Performing VC mixing operation on silicon oxide with the particle size median diameter (D50) of 2.5-5 mu m and magnesium metal powder with the particle size median diameter (D50) of 30-80 mu m, wherein the mixing rotating speed is 800rpm, and the mixing time is 2h, wherein the adding molar ratio of the silicon oxide to the magnesium metal powder material is 1: 0.4. And (3) placing the mixed materials into a box-type furnace for roasting, under the protection of argon atmosphere, keeping the roasting temperature at 750 ℃, keeping the temperature rise rate at 5 ℃/min, keeping the temperature for 2h, and taking out the materials after cooling completely. Adding the obtained material into 3mol/L hydrochloric acid, mixing and stirring, wherein the mass ratio of the obtained material to the hydrochloric acid is 1:5, the stirring rotation speed is 1500rpm, the stirring time is 5 hours, filtering is carried out by adopting a filter press after acid washing is finished, a blast air bellow is used for drying, the dried material and coal tar pitch with the particle size median diameter (D50) of 100-500 mu m are mixed, the mixing mass ratio is 1:0.2, the mixed material is placed into a box furnace for roasting, the atmosphere of argon is protected, the roasting temperature is 700 ℃, the heating rate is 2 ℃/min, the temperature is kept for 5 hours, the material is completely taken out after cooling, the low-oxygen-value silicon oxide/carbon-coated composite negative electrode material is obtained, and the material is crushed, crushed and sieved, and the particle size median particle diameter (D50) of the material is 0.1-100 mu m, namely the finished product silicon oxide composite negative electrode material for the lithium ion battery is obtained.
The negative electrode materials of examples 1 to 6 and comparative examples 1 to 2 were tested by the following methods:
the particle size range and distribution of the material were tested using a malvern laser particle size tester MS 3000.
The specific surface area of the material was tested using a Tristar3000 fully automated specific surface area and porosity analysis from McMac instruments USA.
The morphology, particle size, etc. of the sample were observed using a Hitachi S4800 scanning electron microscope.
Fig. 1 is a schematic structural diagram of a composite negative electrode material of silica prepared by the present invention, the material prepared by the present invention is a composite negative electrode material of silica with a double-layer core-shell structure, and an inner silicate layer is a porous structure for ion migration.
FIG. 2 shows the material structure tested using an X-ray diffractometer X' Pert Pro, PANALYTICAL.
FIG. 3 is an X-ray diffraction pattern of example 1, from which it can be seen that the reacted material contains a certain amount of Mg2SiO4And Mg2SiO3Providing guarantee for forming the porous silicate layer.
Electrochemical cycling performance was tested using the following method: mixing a negative electrode material, a conductive agent and a binder in a solvent according to a mass ratio of 92:2:6, controlling the solid content to be 55%, coating the mixture on a copper foil current collector, and drying to obtain a negative electrode plate; then using a conventional positive plate and 1mol/L LiPF6The battery is characterized by comprising an/EC + DMC (V/V is 1:1) electrolyte, a CeLgard2400 diaphragm and a 18650 cylindrical battery, wherein the housing is assembled by adopting a conventional production process, constant-current charging and discharging are carried out under the rate of 1C, and the charging and discharging voltage is limited to 2.75-4.2V.
Electrochemical test results and grain size test results of the negative electrode materials prepared in examples 1 to 6 and comparative examples 1 and 2 are shown in table 1:
watch 1
The invention adopts a fused salt magnesium thermal method to reduce the silicon oxide, and then carries out carbon coating treatment to prepare the high-efficiency core-shell structure silicon oxide composite negative electrode material, the fused salt magnesium thermal method has obvious advantages compared with the traditional silicon oxide reduction method, firstly, the fused salt magnesium thermal method is easier to control the over-heat release of the material in the reduction process, reduces the reaction temperature, and simultaneously can control the crystal grain enlargement of the silicon oxide; secondly, the molten salt magnesium thermal method can enable the whole reaction system to be in a liquid state or a semi-liquid state, so that the fluidity of the reaction system is increased, the reaction efficiency and the reaction uniformity are improved, and the performance of the prepared material is more excellent; thirdly, the fused salt acts on the surface of the material, and a pore network can be formed on the surface and in the longitudinal depth of the material by utilizing the etching effect of the fused salt, so that the magnesium thermal reduction is carried out at a deeper position in the material, and the structural uniformity of the material is improved. The high-efficiency core-shell structure silicon oxide composite negative electrode material prepared by the invention mainly has the following structural characteristics:
firstly, a molten salt magnesium thermal method is adopted, so that the reaction temperature can be obviously controlled, and the growth of silicon crystal in the material is reduced;
secondly, a layer of Mg with a porous structure can be formed on the surface of the material by adopting a molten salt growth method2SiO3，Mg2SiO4A structural layer;
and thirdly, modifying the surface of the silicon oxide by adopting amorphous carbon at high temperature to prepare the silicon oxide cathode material with a double-layer shell structure.
According to the structural characteristics, the performance of the prepared high-efficiency core-shell structure silicon oxide composite negative electrode material mainly has the following performance characteristics and beneficial effects:
1. the fused salt magnesium thermal method can obviously control the silicon crystal grain enlargement in the material reduction process, simultaneously greatly improves the reaction efficiency and reaction uniformity, and greatly improves the cycle performance of the material along with the improvement of the reaction process;
2. mg with porous structure generated in preparation process2SiO3，Mg2SiO4The structural layer has a good effect on inhibiting the expansion of the material, and the porous structure can effectively improve the ionic conductivity of the material, improve the rate capability of the material and have a remarkable improvement effect on the cycle performance of the material;
3. amorphous carbon structure and porous Mg2SiO3，Mg2SiO4The double-layer coating structure of the structural layer has a better protection effect on active substances in the charge-discharge process, can effectively avoid the active substances from being greatly lost due to the contact with electrolyte, and the carbon structure can improve the conductivity of the material, reduce the specific surface and obviously improve the cycle performance of the material.
4. According to the invention, the fused salt magnesium thermal reaction method is used for preparing the silicon oxide composite negative electrode material, so that a reaction system is converted from solid-solid reaction into solid-liquid reaction or liquid-like reaction, the reaction efficiency and the reaction uniformity are obviously improved, the material has high first effect on the premise of ensuring higher capacity, the prepared silicon oxide negative electrode material with the double-shell structure obviously improves the material cycle performance, the material has excellent overall performance, and meanwhile, the large-scale mass production can be realized.
The present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it is not meant to imply that the present invention must be practiced by relying on the above detailed methods. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitution of each raw material and addition of auxiliary components, selection of specific modes, etc., of the product of the present invention, falls within the scope of protection, transposition and disclosure of the present invention.
Claims (10)
1. The lithium ion battery silicon monoxide composite negative electrode material is characterized by comprising an outer shell layer and an inner shell layer; the outer shell layer is an amorphous carbon layer; the inner shell layer is a porous structure silicate layer.
2. The lithium ion battery siliconoxide composite anode material according to claim 1, wherein the porous structure silicate layer comprises Mg2SiO4And Mg2SiO3The porous channel structure of the porous structure silicate layer is formed by acid etching.
3. A preparation method of a silicon monoxide composite negative electrode material of a lithium ion battery is characterized by comprising the following steps:
(1) preparing a raw material of the silicon monoxide;
(2) uniformly mixing the silicon monoxide prepared in the step (1) with metal magnesium powder and molten salt to obtain a precursor A;
(3) carrying out high-temperature treatment on the precursor A in the step (2) under a protective atmosphere, and carrying out roasting reaction, cooling, acid washing and etching to obtain a semi-finished product B; the acid pickling etching mainly comprises the working procedures of mixing, stirring, filtering and drying a roasted cooling material and an acid solution;
(4) and (3) blending the semi-finished product B and the carbon coating material in the step (3), or coating the semi-finished product B by adopting a gas phase, roasting and carbonizing the semi-finished product B in a protective atmosphere, cooling the semi-finished product B to obtain a silicon oxide/carbon coated composite negative electrode material, and crushing, crushing and screening the silicon oxide/carbon coated composite negative electrode material to obtain the silicon oxide composite negative electrode material of the lithium ion battery.
4. The preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery as claimed in claim 3, wherein in the step (1), the silicon monoxide raw material is silicon monoxide powder with a median particle size D50 of 1-50 μm, and the qualified silicon monoxide raw material is prepared by controlling the particle size and shape by any one of a ball mill, a crusher and a pulverizer, and then sieving and demagnetizing.
5. The preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery as claimed in claim 3, characterized in that in the step (2), the metal magnesium powder is in a solid powder state, the particle size D50 is 0.1-500 μm, and the purity of the metal magnesium powder is more than or equal to 95.0%; the molar ratio of the silicon monoxide to the metal magnesium powder is 1: 0.01-1: 1.
6. The method for preparing the silicon monoxide composite negative electrode material of the lithium ion battery, according to claim 3, wherein in the step (2), the molten salt is in the form of solid particles or powder, and the particle size median diameter D50 of the molten salt is 0.5-1000 μm; the addition mass ratio of the silicon monoxide to the molten salt is 1: 0.1-1: 20.
7. The preparation method of the silicon monoxide composite negative electrode material for the lithium ion battery, according to claim 3, is characterized in that in the step (3), the heating rate is 0.1-20 ℃/min, the temperature is 200-1000 ℃, and the holding time is 0.5-24 h.
8. The preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery as claimed in claim 3, wherein in the step (3), the acid-washing etching comprises normal-temperature etching and heating etching, and the concentration of the acid solution is 0.1-10.0 mol/L.
9. The preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery as claimed in claim 3, wherein in the step (3), the mass ratio of the roasting cooling material to the acid solution is 1: 0.5-1: 15.
10. The preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery, according to claim 3, is characterized in that in the step (4), the temperature of the roasting carbonization treatment is 500-1100 ℃, and the heat preservation time is 2-8 h.
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