CN112701267B - Pre-lithiated silica composite material, negative pole piece, lithium battery and preparation method of pre-lithiated silica composite material - Google Patents
Pre-lithiated silica composite material, negative pole piece, lithium battery and preparation method of pre-lithiated silica composite material Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000002131 composite material Substances 0.000 title claims abstract description 96
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 95
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 52
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 150000002900 organolithium compounds Chemical class 0.000 claims abstract description 14
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000007423 decrease Effects 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 229910001556 Li2Si2O5 Inorganic materials 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 229910007562 Li2SiO3 Inorganic materials 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- 229910020489 SiO3 Inorganic materials 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 3
- 150000002642 lithium compounds Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910002483 Cu Ka Inorganic materials 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 10
- 238000005253 cladding Methods 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052912 lithium silicate Inorganic materials 0.000 abstract description 17
- 239000002002 slurry Substances 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 37
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000000265 homogenisation Methods 0.000 description 7
- 238000009830 intercalation Methods 0.000 description 7
- 230000002687 intercalation Effects 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/58—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
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- 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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a pre-lithiated silica composite material, a negative pole piece, a lithium battery and a preparation method thereof. The preparation method of the pre-lithiated silica composite material comprises the following steps: SiO 2xSiO in-Li @ CxChemical reaction of lithium ions on the surface of Li nucleus with hydroxyl compound to obtain SiOx-Li' @ C, followed by heat treatment; SiO 2x-Li @ C comprises SiOx-a Li core and a carbon layer, said SiOx-Li nuclei with lithium ions distributed inside and on the surface of the silica material; SiO 2x-the content of lithium ions decreases from the inside to the surface of the Li' core; the lithium source for absorbing lithium is an organolithium compound. The water-soluble lithium silicate in the silicon-oxygen composite material prepared by the invention is further coated by the carbon layer by the water-insoluble lithium silicate coated lithium silicate, and in the homogenizing process, the lithium silicate in the silicon-oxygen composite material is insoluble in water, so that the pH value of the slurry cannot be increased, and the gas production of the slurry is inhibited.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a pre-lithiated silica composite material, a negative pole piece, a lithium battery and a preparation method thereof.
Background
The battery core is the most important part of the lithium battery, the pole piece is the core of the battery core and is realized by coating, and the coating is realized by coating the prepared negative electrode slurry on the current collector, so that the performance of the negative electrode slurry determines the coating performance, and it can be said that the quality of a battery has 90% of the determining factor of the slurry. The formula of the slurry, the uniformity of dispersion, the viscosity and stability of the slurry, etc. have a significant impact on the performance of the lithium battery. The active material in the negative electrode slurry, such as a silicon-based negative electrode material, is the main component of the slurry, and determines the coating of the slurry and the performance of the lithium battery.
With the development of electric vehicles, portable electric tools and household appliances, the demand for lithium ion batteries with high energy density, high first coulombic efficiency and high cycle performance is increasing. The theoretical specific capacity of the traditional lithium ion battery cathode material graphite is only 372mAh/g, and the current requirement on high energy density of the cathode is difficult to meet. The silicon-based negative electrode material has higher theoretical lithium intercalation capacity (about 4200mAh/g) and lower lithium intercalation platform, and attracts wide attention.
However, the main problems of the silicon-based negative electrode material are poor conductivity and large volume change (about 300%) during lithium intercalation, resulting in poor cycle performance of the silicon-based negative electrode material. SiO 2xLithium oxide and lithium salt are generated in the lithium intercalation process, so that the volume expansion can be effectively relieved, the cycle performance is improved, but a certain amount of lithium is consumed in the first lithium intercalation process, so that the first coulombic efficiency is low, and the reversible capacity is obviously reduced.
The pre-lithium technology can insert lithium into the SiOxMaterials, formed lithium silicates, e.g. Li4SiO4、Li2SiO3、Li2Si2O5The consumption of positive active lithium is avoided, and the first coulombic efficiency of the silicon monoxide is effectively improved. However, Li formed from the anode material in the prior art4SiO4Readily soluble in water, Li2SiO3Slightly soluble in water, has a great influence on the stability of the material itself, and causes the pH of the aqueous slurry to increase, while a large amount of bubbles are generated, making the homogenization and coating process very difficult. For example, chinese patent document CN111554911A discloses a lithium battery negative electrode material with a lithium content gradient distribution, which sequentially comprises a core, an acid-washing layer and a carbon layer from inside to outside, wherein lithium in the core is uniformly distributed, and lithium in the acid-washing layer is distributed in a concentration gradient manner in which the concentration of lithium in the acid-washing layer decreases from the interface between the core and the acid-washing layer to the edge. According to the examples, the lithium silicate still dissolved in water formed in the core and the pickling layer is dissolved in water during the homogenization process, and a large amount of bubbles are generated, so that the coating cannot be performed or is not uniform. The lithium silicate is alkalescent (the pH value is 11-12), and the pH value of the slurry is increased continuously after the lithium silicate is dissolved in water, so that the generated bubbles are increased continuously, and the bubbles are guidedMaking the coating difficult to perform.
Therefore, the development of a silica composite material which has high coulombic efficiency and high gram volume, is insoluble in water and is easy for large-scale mass production for the first time is a technical problem which needs to be solved in the field.
Disclosure of Invention
The invention aims to overcome the defect that lithium silicate in a silica composite material is dissolved in water to cause difficult coating in the prior art, and provides a pre-lithiated silica composite material, a negative pole piece, a lithium ion battery and a preparation method thereof. Water-soluble lithium silicate (Li) in the silicon-oxygen composite material of the invention2SiO3) By water-insoluble lithium silicate (Li)2Si2O5) Coating, lithium silicate is further coated by carbon layer, and during homogenization, lithium silicate (Li) in the silicon-oxygen composite material2SiO3) Can not be dissolved in water, can not cause the pH value of the slurry to rise, and simultaneously inhibits the slurry from generating gas.
The invention mainly solves the technical problems through the following technical scheme.
The invention provides a preparation method of a pre-lithiated silica composite material, which comprises the following steps: SiO 2xSiO in-Li @ CxChemical reaction of lithium ions on the surface of Li nucleus with hydroxyl compound to obtain SiOx-Li' @ C, and then carrying out heat treatment to obtain the pre-lithiated silica-oxygen composite material;
the SiOx-Li @ C refers to a carbon-coated silica material after lithium absorption, comprising SiOx-a Li core and a carbon layer, said SiOx-Li nuclei with lithium ions distributed inside and on the surface of the silica material;
the SiOxSiO of-Li' @ Cx-in the Li' core, the content of lithium ions decreases from the inside to the surface;
the lithium source for absorbing lithium is an organolithium compound.
The expression of "@" in the present invention is a conventional expression in the art. In particular, "@" generally refers to a core-shell structure, such as SiO in the present inventionx-Li @ C means SiOx-Li is the core and C is the core-shell structure of the shell.
In the present invention, the SiOxFor example, it may be a silicon oxide.
The inventor unexpectedly finds that, after the carbon-coated silica material after lithium absorption and the hydroxyl compound are contacted with each other, lithium ions on the surface layer of the silica material in the carbon-coated silica material after lithium absorption can chemically react with the hydroxyl compound, and a liquid lithium alkoxide compound is generated on the surface of the carbon-coated silica material after lithium absorption. At this time, the content of lithium element on the surface of the silicon-oxygen material in the carbon-coated silicon-oxygen material after lithium absorption is less than that of lithium element in the silicon-oxygen material, and the combination of heat treatment can form water-soluble Li in the silicon-oxygen material2SiO3And surface formed water-insoluble Li2Si2O5Thus, the present invention has been achieved.
The inventors have further studied and found that the above technical problems can be solved by using an organolithium compound as the lithium source for lithium absorption, while the above technical problems cannot be solved by using an inorganic lithium compound, mainly because the carbon-coated silica material is not subjected to a heat treatment after lithium enters the carbon-coated silica material during lithium absorption by using the organolithium compound, and thus a stable phase is not formed, and lithium is still active at this time, and the silica material (SiO) is chemically reactedx-Li core) surface layer, and thereby the present invention has been accomplished. Inorganic lithium must be heat treated to enter the interior of the carbon-coated silica material, and the heat treated lithium is inactive and cannot react with hydroxyl groups.
Thus, the organolithium compound of the present invention can be an organolithium compound conventionally used in the art for preparing a prelithiated silicone material, where the number of carbons in the organolithium compound is 1-8, such as 1, 2, 3, 4, 5, 6, or 8.
In the present invention, the organolithium compound preferably includes alkyl lithium and/or aryl lithium, and specifically includes, for example, one or more of butyl lithium, phenyl lithium, naphthyl lithium, methyl lithium and ethyl lithium, such as phenyl lithium.
In the present invention, the hydroxyl compound may be capable of chemically reacting with lithium ions to form lithium alkoxide, and when the hydroxyl compound is in a liquid state, the hydroxyl compound itself may be used as a reaction solvent, or a solvent miscible with the hydroxyl compound, such as water, may be added as a reaction solvent.
In the present invention, the number of carbons in the hydroxy compound is generally 11 or less, for example, 1 to 6. Specifically, for example, one or more of methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol and glycerol.
In the present invention, it is known to those skilled in the art that the chemical reaction between the carbon-coated silica material after lithium absorption and the hydroxyl compound can be achieved by mixing the carbon-coated silica material after lithium absorption with the hydroxyl compound. Wherein the mixing is performed by washing the carbon-coated silica material after lithium absorption with a hydroxyl compound or a solution containing a hydroxyl compound, or the carbon-coated silica material after lithium absorption is immersed in the hydroxyl compound or the solution containing the hydroxyl compound.
The solvent in the solution of the hydroxyl containing compound is generally miscible with the hydroxyl compound, e.g., water.
In the implementation of the present invention, it is found that the chemical reaction speed of the carbon-coated silica material after lithium absorption and the hydroxyl compound is very rapid, and the mixing time is not particularly limited, for example, within 5 min.
In the present invention, the carbon-coated silica material after lithium absorption generally adopts a material that is conventional in the art. In the art, the carbon layer of the carbon-coated silicon-oxygen material has a thickness of no more than 200nm, and cannot be used as a negative electrode material if the carbon layer is too high, and the radius of the silicon-oxygen material layer is generally 1 to 20 μm. In the present invention, the carbon layer has a thickness of 200nm or less and the silicon oxide layer has a radius of 1 to 20 μm.
In the invention, the carbon-coated silica material can be prepared by adopting a conventional process in the field, and generally comprises the following steps: the silicon oxide is coated by carbon.
Wherein, the carbon coating can be performed by chemical vapor deposition in the prior art. The carbon source gas for chemical vapor deposition includes, for example, one or more of methane, acetylene, and toluene. The temperature of the chemical vapor deposition can be 500-1000 ℃, for example 800 ℃. The holding time of the chemical vapor deposition can be 10min to 10h, such as 1 h. The chemical vapor deposition is generally carried out in a tube furnace. The chemical vapor deposition is generally carried out under an atmosphere of an inert gas, such as argon. The volume ratio of the inert gas to the carbon source gas is, for example, 9: 1.
in the present invention, the lithium absorption generally means that a carbon-coated silica material is mixed with a solution of the organolithium compound. The mixing is generally carried out by stirring.
The mixing time may be conventional in the art and may typically be from 1 to 24 hours, for example 2 hours.
The solvent in the solution of the organolithium compound is generally sufficient to dissolve the organolithium compound, and may include one or more of benzene, cyclohexane, tetrahydrofuran, pentane, diethyl ether, and petroleum ether, for example, diethyl ether.
As can be known to those skilled in the art from the lithium absorption process, the method generally further includes a filtering operation after the lithium absorption, so as to obtain the carbon-coated silica material after the lithium absorption.
In the present invention, the heat treatment process may be a heat treatment process that is conventional in the art.
Wherein the temperature of the heat treatment may be 300 ℃ to 800 ℃, such as 400 ℃, 500 ℃, or 700 ℃.
Wherein the heat preservation time of the heat treatment can be 1-24 h.
The heat treatment may be performed in a tube furnace, a vacuum furnace, or a roller furnace.
The heat treatment is generally carried out under an inert atmosphere, such as argon.
In the present invention, in order to obtain a pre-lithiated silica composite material having a uniform particle size distribution, the heat treatment generally includes sieving. The mesh size of the screen is, for example, 300 mesh.
The invention provides a pre-lithiated silica composite material which is prepared by adopting the preparation method.
The invention provides a pre-lithiated silica composite material which is of a core-shell structure and comprises a core and a shell, wherein the core comprises a core and an intermediate layer;
the core contains Li2SiO3(ii) a The intermediate layer contains Li2Si2O5(ii) a The shell is a carbon layer;
the thickness of the middle layer is 5-1000 nm; the Li in the intermediate layer2Si2O5The mass ratio of (A) to (B) is 1-20% of the total mass of the intermediate layer;
in the pre-lithiated silica-oxygen composite material, the ratio of the mass of lithium element to the total mass of the pre-lithiated silica-oxygen composite material is 5-25%.
In the pre-lithiated silica composite material of the present invention, the silicate in the core is Li2SiO3The lithium content of the material is obviously increased, so that higher first coulombic efficiency can be achieved. If the gas is not generated in the process of homogenizing, the silicate for preparing the inner core is Li2Si2O5The coulomb efficiency of the lithium battery will be significantly reduced.
In the present invention, as will be apparent to those skilled in the art from the pre-lithiated silica composite material, the core or the intermediate layer typically further contains elemental silicon.
In the invention, the ratio of the thicknesses of the core and the middle layer is (1-20): 1.
in the invention, the mass ratio of the core to the intermediate layer is (1-20): 1.
in the present invention, the ratio of the mass of the carbon layer to the total mass of the pre-lithiated silica-oxygen composite material may be conventional in the art, for example, 1 to 10%.
In the present invention, the prelithiated silica composite material was X-ray diffraction measured using Cu-Ka radiation and had lithium silicate Li at 2 θ of 19.1 °, 26.9 °, 33.1 ° and 38.2 °, respectively2SiO3Characteristic peak of (2 θ)Having lithium silicate Li at 24.5 DEG2Si2O5Characteristic peak of (2).
In the invention, the median particle size of the pre-lithiated silica composite material can be 0.5-25 μm.
In the invention, the specific surface area of the pre-lithiated silica composite material can be 0.2-8 m2/g。
The invention also provides a negative pole piece which is prepared by adopting the pre-lithiated silica composite material.
In the invention, the negative pole piece can be prepared by adopting a preparation method commonly used in the field, and generally comprises the following steps: and homogenizing and coating the mixture of the pre-lithiated silica composite material, the binder and the conductive agent to obtain the negative pole piece.
Wherein, in the mixture, the mass ratio of the pre-lithiated silica-oxygen composite material to the binder to the conductive agent is, for example, 70:15: 15.
the invention also provides a lithium battery which comprises the negative pole piece.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the core of the prelithiated silica composite material of the present invention contains a silicate of Li2SiO3The silicate contained in the intermediate layer is Li2Si2O5The outer shell is a carbon layer, lithium pre-inserted into the inner core can reduce the consumption of active lithium ions of the positive electrode in the process of lithium intercalation for the first time, the first coulombic efficiency is improved, and the matching of the core and the middle layer ensures that the pre-lithiated silica-oxygen composite material can not react with water to generate gas during homogenization, the pH value can not be increased, the stability in slurry and the uniform coating are kept, and the carbon layer coated on the surface layer increases the conductivity of the material. The water-insoluble pre-lithiated silica composite material provided by the invention has the characteristics of high first coulombic efficiency, high gram capacity and water insolubility, and can be applied to square batteriesLithium ion batteries such as soft pack batteries and cylindrical batteries; meanwhile, the synthesis method is simple, easy to control and easy to realize large-scale production.
Drawings
FIG. 1 is a schematic structural diagram of a pre-lithiated silica composite of example 1;
fig. 2 is an XRD pattern of the pre-lithiated silica composite of example 1.
Fig. 3 is a first-pass charge-discharge plot of the pre-lithiated silica composite of example 1.
Fig. 4 is a graph of the cycle performance of the pre-lithiated silica composite of example 1.
Fig. 5 is an XRD pattern of the pre-lithiated silica composite of comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
(1) Carbon coating: putting the silicon monoxide into a tube furnace, heating to 800 ℃ under the argon atmosphere, introducing acetylene (the volume ratio of argon to acetylene is 9: 1), and preserving heat for 1 hour to obtain a carbon-coated silica material SiO @ C;
(2) lithium absorption: soaking SiO @ C into a solution containing phenyl lithium, wherein a solvent is diethyl ether, absorbing lithium, continuously stirring the solution for 2 hours, and filtering to obtain a carbon-coated silica material SiO-Li @ C after absorbing lithium;
the thickness of a carbon layer in the carbon-coated silica material after lithium absorption does not exceed 200nm, and the radius of a SiO-Li core is 1-20 mu m;
(3) reaction of SiO-Li @ C with a hydroxy compound: washing SiO-Li @ C with methanol for 5min to eliminate active lithium from the surface of silica material in the carbon coated silica material after absorbing lithium and to obtain SiO-Li' @ C with gradually decreased lithium ion from inside to surface in the SiO-Li core;
(4) and (3) heat treatment: putting the SiO-Li' @ C obtained in the step (3) into a tube furnace, and raising the temperature in an argon atmosphereHeating to 500 deg.C, holding for 1 hr, automatically cooling to room temperature, and sieving with 300 mesh sieve to obtain water-insoluble pre-lithiated silica composite material SiO/Li2SiO3@Li2Si2O5@ C, the structural distribution of which is shown in FIG. 1.
Example 2
Ethanol is adopted for washing in the step (3), and the other preparation process parameters are the same as those in the example 1.
Example 3
The step (3) is washed by propanol, and the rest preparation process parameters are the same as those in the example 1.
Example 4
The temperature of the heat treatment in the step (4) was 400 ℃, and the other preparation process parameters were the same as in example 1.
Example 5
The temperature of the heat treatment in the step (4) was 700 ℃, and the other preparation process parameters were the same as in example 1.
Comparative example 1
In the step (3), alcohol washing treatment is not adopted, the carbon-coated silica material SiO-Li @ C after lithium absorption obtained by filtration is directly subjected to heat treatment, and other process parameters are the same as those in the example 1.
Comparative example 2
In the step (3), ether is used to replace an alcohol compound to wash the carbon-coated silica material SiO-Li @ C after the lithium absorption obtained by filtration, and the other process parameters are the same as those in the example 1.
Effect example 1
The performance of the pre-lithiated silica composite materials of examples 1 to 5 and comparative examples 1 to 2 was tested as follows.
(1) XRD characterization of prelithiated silica composites
The XRD pattern of the prelithiated silica composite of example 1 is shown in figure 2. As can be seen from fig. 2, the prelithiated silica material in this example has lithium silicate Li at 2 θ of 19.1 °, 26.9 °, 33.1 ° and 38.2 °, respectively2SiO3Has a characteristic peak of lithium silicate Li at 24.5 DEG 2 theta2Si2O5Characteristic peak of (2).
Examples 2 to 5 Pre-lithiated silica composite MaterialXRD characterization of the materials showed that they all contained Li in accordance with example 12SiO3Characteristic peak of (1) and lithium silicate Li2Si2O5Characteristic peak of (2). Among them, the intensity of the characteristic peak of example 4 is lower than that of example 1, indicating that Li2SiO3And Li2Si2O5Is not very crystalline. The intensity of the characteristic peak in example 5 is higher than that in example 1, indicating that Li2SiO3And Li2Si2O5The crystallinity is stronger and the grain size is larger.
The XRD pattern of the prelithiated silica composite of comparative example 1 is shown in FIG. 5, which contains only Li2SiO3Characteristic peak of (1) without Li2Si2O5Characteristic peak of (A), indicating that Li is absent2Si2O5And (4) generating. The XRD test results of comparative example 2 are the same as those of comparative example 1.
According to XRD test results and the experimental results in the following table 2, the structure of the pre-lithiated silica composite material prepared in the embodiments 1 to 5 of the present invention is a core-shell structure, and the pre-lithiated silica composite material includes an inner core and an outer core, the inner core includes a core and an intermediate layer, and the core includes Li2SiO3The intermediate layer contains Li2Si2O5The shell is a carbon layer. The thickness of the intermediate layer is 5-1000 nm, and Li in the intermediate layer2Si2O5The mass ratio of (A) to (B) in the total mass of the intermediate layer is 1-20%; in the pre-lithiated silica-oxygen composite material, the ratio of the mass of the lithium element to the total mass of the pre-lithiated silica-oxygen composite material is 5-25%. The thickness ratio of the core to the intermediate layer is (1-20): 1.
(2) pH testing of prelithiated silica composites
10g of SiO/Li in examples 1 to 5 and comparative examples 1 to 2 was used2SiO3@Li2Si2O5@ C was dispersed in 100mL of water with constant stirring. The pH value was measured at 1min of stirring and after 24h of stirring. And the generation of bubbles in the solution after stirring for 24 hours was visually observed to simulate the homogenization process, and the test results are shown in table 2 below.
As can be seen from the test results in Table 2, examples 1 to 3 and experimentsThe pH value in the dispersion of the prelithiated silica composite material of example 5 did not increase with the extension of the stirring time, and no bubble was generated even after stirring for 24 hours, indicating that SiO/Li2SiO3@Li2Si2O5@ C is insoluble in water. The pH in the dispersion of the pre-lithiated silica composite in example 4 was slightly higher than the other examples, slightly increasing over time, and small bubbles were generated after 24h of stirring, indicating that the material was slightly soluble in water.
While the dispersion liquid of comparative example 1 and comparative example 2 continuously generated bubbles, and the bubbles increased with the extension of the stirring time, indicating that the composite material SiO/Li prepared in comparative example 1 and comparative example 22SiO3@ C is soluble in water and reacts significantly with water. However, during the subsequent homogenization, a large amount of bubbles are generated, so that the coating cannot be performed.
(4) Battery performance testing
The pre-lithiated silica-oxygen composite material obtained in example 1 was prepared as a pre-lithiated silica-oxygen composite material: binder (PAA): and (4) homogenizing and coating the conductive agent (SP) at a ratio of 70:15:15 to obtain the negative pole piece. And the negative pole piece is assembled into a half-cell, and a charge-discharge test and a cycle stability test are carried out at 0.1C, and the result is shown in figures 3 and 4, and figure 3 is a first-turn charge-discharge curve diagram of the pre-lithiated silica composite material of the embodiment 1. Fig. 4 is a graph of the cycle performance of the pre-lithiated silica composite of example 1. The test results are shown in table 2 below.
Examples 2-5 and comparative examples 1-2 negative electrode sheets were prepared according to the same method and parameters as in example 1, and assembled into half cells for charge and discharge testing and cycling stability testing at 0.1C, with the test results shown in table 2 below.
TABLE 2
Note: the cell performance of the composite was not measured because it was difficult to homogenize and it was impossible to produce a half cell because an acceptable silica composite was not formed.
From the above experimental results, it can be seen that the water-insoluble pre-lithiated silica composite material SiO/Li obtained by the preparation method of the present invention2SiO3@Li2Si2O5@ C has excellent electrochemical properties, is insoluble in water, does not generate bubbles, and is easy to homogenize and coat.
According to the pre-lithiated silica composite material provided by the embodiments 1 to 5, the carbon-coated silica material subjected to lithium absorption and a hydroxyl compound are subjected to a chemical reaction to generate lithium alkoxide, for example, the lithium concentration on the surface and inside of the silica material is regulated and controlled in a washing manner, and then the lithium alkoxide is subjected to heat treatment to obtain the silica composite material with the core surface containing Li2Si2O5The core of the core contains Li2SiO3The outer coating layer of the pre-lithiated silicon-oxygen composite material is a carbon layer formed by organic matter vapor deposition. Lithium pre-inserted into the core can reduce the consumption of positive active lithium ions in the process of lithium intercalation for the first time, improve the first coulombic efficiency, and Li on the surface of the core2Si2O5Insoluble in water, and the Li of the core is removed during homogenization2SiO3The slurry is separated from water, so that the pH value of the slurry is not increased, and the gas production of the slurry is inhibited; meanwhile, the carbon layer coated on the surface layer increases the conductivity of the material.
Therefore, the pre-lithiated silica composite material provided by the invention has the characteristics of high first coulombic efficiency, high gram capacity and water insolubility, and can be applied to lithium ion batteries such as square batteries, soft-package batteries and cylindrical batteries; meanwhile, the synthesis method is simple, easy to control and easy to realize large-scale production.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (25)
1. The preparation method of the pre-lithiated silica composite material is characterized by comprising the following steps of:
after the lithium ions on the surface of the SiO-Li core in the SiO-Li @ C chemically react with a hydroxyl compound, SiO-Li' @ C is obtained, and then the pre-lithiated silica composite material is obtained after heat treatment;
the SiO-Li @ C is a carbon-coated silica material after lithium absorption, and comprises a SiO-Li core and a carbon layer, wherein lithium ions in the SiO-Li core are distributed in the silica material and on the surface of the silica material;
in the SiO-Li 'core of the SiO-Li' @ C, the content of lithium ions decreases from the inside to the surface;
the lithium source for absorbing lithium is an organic lithium compound;
the organic lithium compound is alkyl lithium and/or aryl lithium;
the number of carbons in the hydroxy compound is 1 to 11;
the pre-lithiated silica composite material is of a core-shell structure and comprises a core and a shell, wherein the core comprises a core and an intermediate layer; the silicate contained in the core is Li2SiO3(ii) a The silicate contained in the intermediate layer is Li2Si2O5(ii) a The shell is a carbon layer.
2. The method of preparing a prelithiated silica composite according to claim 1, wherein the organolithium compound is one or more of butyl lithium, phenyl lithium, naphthyl lithium, methyl lithium, and ethyl lithium;
and/or the number of carbons in the hydroxyl compound is 1-6;
and/or the chemical reaction is realized by washing the carbon-coated silica material after lithium absorption by the hydroxyl compound or the solution containing the hydroxyl compound, or the carbon-coated silica material after lithium absorption is immersed in the hydroxyl compound or the solution containing the hydroxyl compound.
3. The method of preparing a prelithiated silicone-oxygen composite material of claim 1, wherein the hydroxyl compound is one or more of methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, and glycerol.
4. The method of preparing a prelithiated silicone oxygen composite material of claim 1, wherein the carbon layer in the SiO-Li @ C has a thickness of no more than 200 nm;
and/or the radius of the SiO-Li core in the SiO-Li @ C is 1-20 mu m;
and/or the preparation method of the carbon-coated silicon oxygen material comprises the following steps: the silicon oxide is coated by carbon.
5. The method of preparing a prelithiated silicone oxygen composite material of claim 4, wherein said carbon cladding is by chemical vapor deposition.
6. The method of preparing a prelithiated silicone oxygen composite material of claim 5, wherein the chemical vapor deposited carbon source gas comprises one or more of methane, acetylene, and toluene.
7. The method of preparing a pre-lithiated silica composite material of claim 5, wherein the temperature of the chemical vapor deposition is from 500 ℃ to 1000 ℃.
8. The method of preparing a prelithiated silicone oxygen composite material of claim 7, wherein the chemical vapor deposition temperature is 800 ℃.
9. The method of preparing a pre-lithiated silica composite material of claim 5, wherein the time for the thermal insulation of the chemical vapor deposition is 10min to 10 hours.
10. The method of preparing a prelithiated silicone oxygen composite material of claim 9, wherein the chemical vapor deposition is carried out for an incubation time of 1 hour.
11. The method of preparing a prelithiated silicone oxygen composite material of claim 5, wherein said chemical vapor deposition is performed in a tube furnace.
12. The method of preparing a prelithiated silicone oxygen composite material of claim 6, wherein said chemical vapor deposition is carried out under an inert gas atmosphere, and the volume ratio of said inert gas to said carbon source gas is 9: 1.
13. the method of preparing a prelithiated silicone oxygen composite material of claim 12, wherein the inert gas is argon.
14. The method of preparing a prelithiated silicone-oxygen composite material of claim 1, wherein said lithium-absorbing is a mixture of a carbon-coated silicone-oxygen material and a solution of said organolithium compound;
wherein the solvent of the solution of the organolithium compound comprises one or more of benzene, cyclohexane, tetrahydrofuran, pentane, diethyl ether and petroleum ether.
15. The method of preparing a prelithiated silicone-oxygen composite material of claim 14, wherein the mixing time is 1 to 25 hours.
16. The method of preparing a prelithiated silicone oxygen composite material of claim 15, wherein the time of mixing is 2 hours.
17. The method of preparing the prelithiated silicone-oxygen composite material of any of claims 1 to 16, wherein the temperature of the heat treatment is from 300 ℃ to 800 ℃;
and/or the heat preservation time of the heat treatment is 1-24 h;
and/or the heat treatment is carried out in a tube furnace, a vacuum furnace or a roller furnace;
and/or, the heat treatment is carried out under an inert atmosphere;
and/or, said heat treatment is followed by sieving.
18. The method of preparing a prelithiated silicone oxygen composite material of claim 17, wherein the temperature of the heat treatment is 400 ℃, 500 ℃, or 700 ℃;
and/or, the heat treatment is carried out under an argon atmosphere;
and/or the screened mesh number is 300 meshes.
19. A pre-lithiated silica composite material characterized by being produced by the method for producing a pre-lithiated silica composite material according to any one of claims 1 to 18.
20. The pre-lithiated silica composite material is characterized by having a core-shell structure and comprising a core and a shell, wherein the core comprises a core and an intermediate layer; the silicate contained in the core is Li2SiO3(ii) a The silicate contained in the intermediate layer is Li2Si2O5(ii) a The shell is a carbon layer; the thickness of the intermediate layer is 5-1000 nm, and Li in the intermediate layer2Si2O5The mass ratio of (A) to the total mass of the intermediate layer is 1-20%; in the pre-lithiated silica-oxygen composite material, the ratio of the mass of the lithium element to the total mass of the pre-lithiated silica-oxygen composite material is 5-25%.
21. The prelithiated silicone-oxygen composite material of claim 20, wherein said core or said intermediate layer further comprises elemental silicon;
and/or the ratio of the thicknesses of the core and the middle layer is (1-20): 1;
and/or the mass ratio of the core to the middle layer is (1-20): 1;
and/or the ratio of the mass of the carbon layer to the total mass of the pre-lithiated silica-oxygen composite material is 1-10%;
and/or in the pre-lithiated silica composite material, 2 theta in X-ray diffraction measurement of Cu-Ka rays has Li at 19.1 degrees, 26.9 degrees, 33.1 degrees and 38.2 degrees2SiO3Has Li at 24.5 DEG 2 theta2Si2O5Characteristic peak of (a);
and/or the median particle size of the pre-lithiated silica composite material is 0.5-25 μm;
and/or the specific surface area of the pre-lithiated silica-oxygen composite material is 0.2-8 m2/g。
22. A negative electrode plate, which is characterized by being prepared from the pre-lithiated silica composite material as claimed in any one of claims 19 to 21.
23. The negative electrode tab of claim 22, wherein the negative electrode tab preparation method comprises the steps of: and homogenizing and coating the mixture of the pre-lithiated silica composite material, the binder and the conductive agent to obtain the negative pole piece.
24. The negative electrode tab of claim 23, wherein the pre-lithiated silica composite, binder, and conductive agent in the mixture are present in a mass ratio of 70:15: 15.
25. a lithium battery comprising the negative electrode tab according to any one of claims 22 to 24.
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| CN113871606A (en) * | 2021-12-02 | 2021-12-31 | 北京胜能能源科技有限公司 | Silica anode material and preparation method and application thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111900366A (en) * | 2020-07-02 | 2020-11-06 | 有研资源环境技术研究院(北京)有限公司 | SiO containing lithiumxMethod for preparing powder |
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| US11876220B2 (en) * | 2019-12-30 | 2024-01-16 | Shanghai Shanshan Tech Co., Ltd. | Silicon-based anode material for secondary battery and preparation method thereof, secondary battery |
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