WO2021023305A1 - 一种硅基负极材料及其制备方法和应用 - Google Patents

一种硅基负极材料及其制备方法和应用 Download PDF

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WO2021023305A1
WO2021023305A1 PCT/CN2020/107849 CN2020107849W WO2021023305A1 WO 2021023305 A1 WO2021023305 A1 WO 2021023305A1 CN 2020107849 W CN2020107849 W CN 2020107849W WO 2021023305 A1 WO2021023305 A1 WO 2021023305A1
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silicon
negative electrode
borate
powder
based negative
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French (fr)
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赵伟
李素丽
袁号
唐伟超
李俊义
徐延铭
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珠海冠宇电池股份有限公司
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Definitions

  • This application relates to the technical field of lithium ion batteries, and in particular to a silicon-based negative electrode material and its preparation method and application.
  • Lithium-ion batteries have the characteristics of high energy density, long cycle life and environmental friendliness. They have been widely used in electronic products such as mobile communication devices, notebook computers, and digital cameras, and are gradually playing a role in the fields of electric vehicles and energy storage.
  • the anode material is one of the key materials of lithium-ion batteries.
  • the most widely used commercial lithium-ion battery anode material is graphite. Its theoretical specific capacity is 372mAh/g, which can no longer meet the requirements of high-energy density lithium-ion batteries.
  • the theoretical specific capacity of silicon-based anode materials can reach 4200mAh/g, and the replacement of graphite anodes can significantly increase the energy density of the battery. It is a very promising next-generation anode material.
  • silicon-based materials will undergo huge volume changes during the process of deintercalating lithium, resulting in poor cycle performance and low first charge and discharge efficiency.
  • the current solution is mainly to nano-size silicon-based materials and composite silicon-based materials with carbon-based materials, which can improve the performance of silicon-based materials to a certain extent.
  • the performance of current silicon-based materials still needs to be further improved.
  • the purpose of this application is to provide a silicon-based negative electrode material and its preparation method and application.
  • the silicon-based negative electrode material can improve the cycle performance, first charge and discharge efficiency and lithium ion conduction of the silicon-based material. Performance, thereby improving the cycle life of lithium-ion batteries, increasing the energy density of lithium-ion batteries, and improving the rate performance of lithium-ion batteries.
  • This application provides a silicon-based negative electrode material, wherein the silicon-based negative electrode material has a core-shell structure, and a borate is grafted on the outer surface of the shell layer; the material forming the core includes silicon powder and/or Silica powder, and the material forming the shell includes lithium borate.
  • the weight percentage of the borate in the silicon-based negative electrode material is 0.01-2 wt%.
  • the average particle size of the core body is 1 nm-10 ⁇ m.
  • the thickness of the shell layer is 0.1-100 nm.
  • the boric acid ester is selected from one or more compounds having the structure represented by formula (1):
  • n is an integer between 0-10000
  • R 0 is selected from H, alkyl, aryl or one or more F substituted aryl groups
  • n, y1, y2, y3, and y4 respectively represent the average degree of polymerization of the corresponding repeating unit.
  • R 0 is selected from H, C 1-6 alkyl, -C 6 H 5 or one or more F-substituted -C 6 H 5 .
  • the R 1 and R 2 groups in the boric acid ester will be partially hydrolyzed, and the B atom will be bonded to the surface of the inorganic lithium borate, thereby being grafted onto the surface of the lithium borate to prepare the silicon-based negative electrode material .
  • Alkyl used alone or as a suffix or prefix in this application is intended to include straight lines having 1 to 20, preferably 1 to 6 carbon atoms (or if a specific number of carbon atoms is provided, that specific number). Chain or branched saturated aliphatic hydrocarbon group.
  • C 1-6 alkyl means a straight or branched chain alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms
  • C 2-4 alkyl means having 2, 3, or 4 A straight or branched chain alkyl group of three carbon atoms.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.
  • Alkenyl as used alone or as a suffix or prefix in this application is intended to include inclusions having 2 to 20, preferably 2-6 carbon atoms (or if a specific number of carbon atoms is provided, that specific number) Alkenyl is a linear or branched aliphatic hydrocarbon group.
  • C 2-6 alkenyl means an alkenyl group having 2, 3, 4, 5, or 6 carbon atoms.
  • alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, 3 -Methylbut-1-enyl, 1-pentenyl, 3-pentenyl and 4-hexenyl.
  • aryl used in this application refers to an aromatic ring structure composed of 5 to 20 carbon atoms.
  • aromatic ring structures containing 5, 6, 7 and 8 carbon atoms which can be monocyclic aromatic groups such as phenyl; those containing 8, 9, 10, 11, 12, 13 or 14 carbon atoms
  • the ring structure can be polycyclic, such as naphthyl, anthryl, and phenanthryl.
  • aryl also includes polycyclic ring systems having two or more rings in which two or more carbons are shared by two adjacent rings (the rings are "fused rings"), in which at least One ring is aromatic and the other ring can be, for example, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and/or heterocyclyl.
  • polycyclic rings include, but are not limited to, 2,3-dihydro-1,4-benzodioxane and 2,3-dihydro-1-benzofuran.
  • alkyl in the term “alkoxy” used in this application is the same as above.
  • the specific surface area of the silicon-based negative electrode material is 0.5-1000 m 2 /g.
  • This application also provides a method for preparing the aforementioned silicon-based negative electrode material, which includes the following steps:
  • step 2) Mix the material with the core-shell structure of step 1) with boric acid ester, organic solvent and water, and react to prepare the silicon-based negative electrode material.
  • step 1) the mixing is performed in a ball mill, for example, and the mixing time is 2-24 hours.
  • the calcination temperature is 800-1000°C, and the calcination time is 0.1-12h.
  • the lithium borate powder is melted at a high temperature and then coated on the surface of the silicon powder and/or silousite powder to obtain a material with a core-shell structure.
  • step 1) the mass ratio of the silicon powder and/or silousite powder to lithium borate is (95-99.9): (0.1-5).
  • the inert atmosphere refers to an atmosphere that does not react with the reaction system, such as nitrogen, an inert gas, or the like.
  • the organic solvent is selected from at least one of ethanol, acetone, toluene and xylene.
  • step 2) the temperature of the reaction is 20-100° C., and the time of the reaction is 0.1-24 h; the reaction is carried out under stirring conditions, for example.
  • step 2) the mass ratio of borate, organic solvent and water is (0.1-99.8%): (0.1-99.8%): (0.1-99.8%).
  • step 2) the mass ratio of the material with core-shell structure to borate in step 1) is (1 ⁇ 80): (99 ⁇ 20); in the final product prepared, the mass ratio of borate The content accounts for 0.01-2wt%.
  • the borate will be grafted on the surface of the shell layer during the reaction process.
  • the surface of the shell layer is fully grafted with borate, no more grafting reactions can take place.
  • the amount of borate in the final product The content depends on the molecular weight of the borate. The higher the molecular weight of the borate, the greater the proportion of borate in the final product.
  • the method further includes a post-processing step: filtering or centrifuging the mixed system after the reaction to remove liquid, washing with an organic solvent or water, and drying.
  • the method specifically includes the following steps:
  • S1 Mix silicon powder and/or silicon oxide powder with lithium borate powder uniformly to obtain a mixed powder, ball mill the mixed powder with a ball mill for 2-24 hours, and then calcinate at 800-1000°C for 0.1- under an inert atmosphere 12h, obtaining a material with a core-shell structure, the material forming the core includes a silicon powder body and/or a silica powder, and the material forming the shell includes lithium borate;
  • the application also provides a silicon-based anode material, which is prepared by the above-mentioned method.
  • the application also provides the application of the above-mentioned silicon-based negative electrode material in liquid lithium ion batteries or gel state lithium ion batteries or solid state lithium ion batteries.
  • the present application also provides a liquid lithium ion battery, which includes a positive pole piece, a negative pole piece, a separator, and an electrolyte, wherein the negative pole piece is prepared by using the aforementioned silicon-based negative electrode material.
  • the present application also provides a gel state lithium ion battery, the gel state lithium ion battery includes a positive pole piece, a negative pole piece and a gel electrolyte membrane, wherein the negative pole piece adopts the aforementioned silicon-based negative electrode material Prepared.
  • the present application also provides a solid-state lithium ion battery, which includes a positive pole piece, a negative pole piece and a solid electrolyte membrane, wherein the negative pole piece is prepared by using the aforementioned silicon-based negative electrode material.
  • the present application provides a silicon-based negative electrode material and a preparation method and application thereof.
  • the surface of the silicon-based negative electrode material has a lithium borate coating layer, which can effectively reduce side reactions on the negative electrode surface and improve the first charge and discharge efficiency of the material;
  • Figure 1 is a schematic diagram of the structure of a silicon-based negative electrode material.
  • borate esters B1 to B8 used in the following examples are shown in Table 1 below:
  • borate B1, toluene and water are uniformly mixed to form a mixed solution, where water accounts for 0.1% of the mixed solution by mass, toluene accounts for 0.1% of the mixed solution, and borate B1 accounts for 99.8% of the mixed solution;
  • 1 part by mass of M1 is added to 99 parts by mass of the above mixed solution, kept at 100° C., stirred for 24 hours, filtered to remove the liquid, washed with toluene, and dried to obtain the silicon-based negative electrode material of the present application.
  • the negative electrode is prepared from silicon powder with an average particle diameter of 1nm, and assembled with lithium cobalt oxide positive electrode, polyethylene diaphragm and conventional commercial electrolyte of lithium ion battery to form a liquid lithium ion battery, and its rate performance is tested (test method: test under 3C rate Discharge capacity retention rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • Example 1 The M1 in Example 1 was used to prepare a negative electrode, combined with a lithium cobalt oxide positive electrode, a polyethylene diaphragm, and a conventional commercial electrolyte of a lithium ion battery to assemble a liquid lithium ion battery, and test its rate performance (test method: test the discharge capacity retention at 3C rate Rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • a material with a core-shell structure (denoted as M2) is obtained, the material forming the core includes silica powder, the material forming the shell includes lithium borate, and the thickness of the shell layer is 100 nm.
  • borate B2 acetone and water are uniformly mixed to form a mixed solution, where water accounts for 99.8% of the mixed solution by mass, acetone accounts for 0.1% of the mixed solution, and borate B2 accounts for 0.1% of the mixed solution; Then 10 parts by mass of M2 is added to 90 parts by mass of the above-mentioned mixed solution, kept at 20° C., stirred for 0.1 h, centrifuged to remove the liquid, washed with water, and dried to obtain the silicon-based negative electrode material of the present application.
  • a negative electrode was prepared from silousite powder with an average particle size of 10 ⁇ m, and assembled with lithium iron phosphate positive electrode, polyethylene ceramic composite diaphragm and conventional commercial electrolyte of lithium ion battery to form a liquid lithium ion battery, and its rate performance was tested (test method: Test the discharge capacity retention rate under 3C rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • Example 2 The M2 in Example 2 was used to prepare a negative electrode, combined with a lithium iron phosphate positive electrode, a polyethylene ceramic composite diaphragm, and a lithium-ion battery conventional commercial electrolyte to assemble a liquid lithium-ion battery, and test its rate performance (test method: test discharge at 3C rate Capacity retention rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • a material with a core-shell structure (denoted as M3) is obtained, the material forming the core includes silica powder, the material forming the shell includes lithium borate, and the thickness of the shell layer is 15 nm.
  • borate B3, ethanol and water are uniformly mixed to form a mixed solution, where water accounts for 50% of the mixed solution by mass, ethanol accounts for 48% of the mixed solution, and borate B3 accounts for 2% of the mixed solution;
  • 50 parts by mass of M3 is added to 50 parts by mass of the above mixed solution, kept at 50° C., stirred for 1 hour, filtered to remove the liquid, washed with ethanol, and dried to obtain the silicon-based negative electrode material of the present application.
  • a negative electrode is prepared from silousite powder with an average particle size of 1 ⁇ m, and a nickel-cobalt-manganese (NCM622) ternary positive electrode and PVDF gel electrolyte membrane are used to assemble a gel-state lithium-ion battery.
  • the rate performance is tested (test method: Test the discharge capacity retention rate under 3C rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • Example 3 The M3 in Example 3 was used to prepare a negative electrode, combined with a nickel-cobalt-manganese (NCM622) ternary positive electrode and PVDF gel electrolyte membrane to assemble a gel-state lithium ion battery, and test its rate performance (test method: test discharge at 3C rate) Capacity retention rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • NCM622 nickel-cobalt-manganese
  • the mixed powder is ball milled with a ball mill for 6 hours, and then calcined at 850°C for 8 hours under the protection of an inert atmosphere.
  • the material of the core-shell structure (denoted as M4), the material forming the core includes silicon powder, the material forming the shell includes lithium borate, and the thickness of the shell layer is 3 nm.
  • borate B4, xylene and water are evenly mixed to form a mixed solution, where the mass fraction of water in the mixed solution is 98%, the mass fraction of xylene in the mixed solution is 0.5%, and the mass fraction of borate B4 in the mixed solution is 1.5 %; then add 40 parts by mass of M4 to 60 parts by mass of the above-mentioned mixed solution, keep at 30°C, stir for 0.5h, filter to remove the liquid, wash with ethanol, and dry to obtain the silicon-based negative electrode material of the present application.
  • a negative electrode was prepared from silicon powder with an average particle size of 50nm, combined with a nickel-cobalt-manganese ternary positive electrode and a sulfide solid electrolyte membrane to assemble a solid-state lithium-ion battery, and its rate performance was tested (test method: test the discharge capacity retention rate under 3C rate) ), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge and discharge efficiency and energy density.
  • Example 4 The M4 in Example 4 was used to prepare a negative electrode, combined with a nickel-cobalt-manganese ternary positive electrode and a sulfide solid electrolyte membrane to assemble a solid lithium-ion battery, and test its rate performance (test method: test the discharge capacity retention rate at a rate of 3C), test Its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge and discharge efficiency and energy density.
  • silica powder with an average particle size of 500nm and 1.5 parts of lithium borate powder are mixed uniformly to obtain a mixed powder.
  • the mixed powder is ball milled with a ball mill for 5 hours, and then calcined at 920°C for 1.5 hours under the protection of an inert atmosphere.
  • a material with a core-shell structure (denoted as M5) can be obtained, the material forming the core includes silica powder, the material forming the shell includes lithium borate, and the thickness of the shell layer is 2.5 nm.
  • borate B5, borate B6, ethanol and water are evenly mixed to form a mixed solution, where water accounts for 20% of the mixed solution mass fraction, ethanol accounts for 75% of the mixed solution mass fraction, and borate B5 accounts for the mass fraction of the mixed solution.
  • the fraction is 5%, and the mass fraction of borate B6 in the mixed solution is 5%; then add 80 parts by mass of M5 to 20 parts by mass of the above-mentioned mixed solution, keep at 50°C, stir for 3h, filter to remove the liquid, and use ethanol/water
  • the mixed solvent is washed and dried to obtain the silicon-based negative electrode material of the present application.
  • a negative electrode was prepared from silousite powder with an average particle size of 500nm, and a solid-state lithium ion battery was assembled with a nickel-cobalt-manganese ternary positive electrode and a sulfide solid electrolyte membrane to test its rate performance (test method: test discharge capacity at 3C rate) Retention rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • Example 5 The M5 in Example 5 was used to prepare a negative electrode, combined with a nickel-cobalt-manganese ternary positive electrode and a sulfide solid electrolyte membrane to assemble a solid lithium-ion battery, and test its rate performance (test method: test the discharge capacity retention rate at a rate of 3C), test Its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge and discharge efficiency and energy density.
  • a material with a core-shell structure (denoted as M6), the material forming the core includes silicon powder, the material forming the shell includes lithium borate, and the thickness of the shell layer is 0.5 nm.
  • borate B7, borate B8, ethanol and water are evenly mixed to form a mixed solution, where water accounts for 10% of the mixed solution mass fraction, ethanol accounts for 77% of the mixed solution mass fraction, and borate B7 accounts for the mass fraction of the mixed solution.
  • the fraction is 10%, and the mass fraction of borate B8 in the mixed solution is 3%; then 60 parts by mass of M6 are added to 40 parts by mass of the above-mentioned mixed solution, kept at 70°C, stirred for 1 hour, filtered to remove the liquid, and washed with ethanol. After drying, the silicon-based anode material of the present application can be obtained.
  • a negative electrode was prepared from silicon powder with an average particle size of 5nm, and a lithium cobalt oxide positive electrode and PVDF gel electrolyte membrane were used to assemble a gel lithium ion battery to test its rate performance (test method: test the discharge capacity retention at a rate of 3C) Rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • Example 6 The M6 in Example 6 was used to prepare a negative electrode, combined with a lithium cobalt oxide positive electrode and PVDF gel electrolyte membrane to assemble a gel state lithium ion battery, and test its rate performance (test method: test the discharge capacity retention rate at a rate of 3C), Test its cycle performance under 25°C, 1C/1C charge-discharge conditions, test its first charge-discharge efficiency and energy density.
  • a material with a core-shell structure (denoted as M7) can be obtained, the material forming the core includes silica powder, the material forming the shell includes lithium borate, and the thickness of the shell layer is 2 nm.
  • borate B1, borate B3, borate B6, ethanol and water are mixed uniformly to form a mixed solution, where water accounts for 50% of the mixed solution mass fraction, ethanol accounts for 44% of the mixed solution mass fraction, borate B1 occupies 2% of the mass fraction of the mixed solution, borate B3 occupies 2% of the mass fraction of the mixed solution; borate B6 occupies 2% of the mass fraction of the mixed solution; then 50 parts by mass of M7 is added to 50 parts by mass of the above-mentioned mixture In the solution, keep at 45° C., stir for 5 hours, filter to remove the liquid, wash with ethanol, and dry to obtain the silicon-based negative electrode material of the present application.
  • test method Test the discharge capacity retention rate at 3C rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • the negative electrode is prepared from silicon oxide powder with an average particle size of 100nm, combined with lithium iron phosphate positive electrode, polypropylene PP/polyethylene PE/polypropylene PP three-layer composite diaphragm and conventional lithium ion battery commercial electrolyte to assemble into liquid lithium Ion battery, test its rate performance (test method: test discharge capacity retention rate under 3C rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge and discharge efficiency and energy density.
  • Example 7 The M7 in Example 7 was used to prepare a negative electrode, combined with a lithium iron phosphate positive electrode, a polypropylene PP/polyethylene PE/polypropylene PP three-layer composite diaphragm and a conventional lithium ion battery commercial electrolyte to assemble a liquid lithium ion battery, and test it Rate performance (test method: test discharge capacity retention rate under 3C rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge and discharge efficiency and energy density.
  • a material with a core-shell structure (denoted as M8), the material forming the core includes silicon powder, the material forming the shell includes lithium borate, and the thickness of the shell layer is 8 nm.
  • borate B2, borate B5, borate B8, acetone and water are uniformly mixed to form a mixed solution, where water accounts for 2% of the mixed solution mass fraction, acetone accounts for 76% of the mixed solution mass fraction, borate
  • the mass fraction of B2 in the mixed solution is 5%
  • the mass fraction of borate B5 in the mixed solution is 10%
  • the mass fraction of borate B8 in the mixed solution is 7%
  • 50 parts by mass of M8 are added to 50 parts by mass of the above mixture In the solution, keep 65° C., stir for 2 hours, filter to remove the liquid, wash with water, and dry to obtain the silicon-based negative electrode material of the present application.
  • a negative electrode was prepared from silicon powder with an average particle size of 20nm, combined with a nickel-cobalt-manganese ternary (NCM523) positive electrode, a polyethylene ceramic coating composite diaphragm and a conventional lithium-ion battery commercial electrolyte to assemble a liquid lithium-ion battery.
  • Rate performance test method: test discharge capacity retention rate under 3C rate
  • test its cycle performance under 25°C, 1C/1C charge and discharge conditions
  • test its first charge and discharge efficiency and energy density test its first charge and discharge efficiency and energy density.
  • Example 8 The M8 in Example 8 was used to prepare a negative electrode, combined with a nickel-cobalt-manganese ternary (NCM523) positive electrode, a polyethylene ceramic coating composite diaphragm and a conventional lithium-ion battery commercial electrolyte to assemble a liquid lithium-ion battery, and its rate performance Test method: test the discharge capacity retention rate under 3C rate), test its cycle performance under 25°C, 1C/1C charge and discharge conditions, test its first charge-discharge efficiency and energy density.
  • NCM523 nickel-cobalt-manganese ternary
  • the negative electrode plate made of silicon-based negative electrode material will undergo a cross-linking reaction during the high-temperature baking of the electrode piece to form cross-links between the silicon-based negative electrode material particles, effectively ensuring the structural integrity of the silicon negative electrode electrode during the cycle. Thereby improving the cycle performance of the battery.

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Abstract

本申请提供了一种硅基负极材料及其制备方法和应用，所述硅基负极材料表面具有硼酸锂包覆层，包覆层可以有效减弱负极表面副反应，提高材料的首次充放电效率；硼酸锂包覆层与具有特定结构的硼酸酯之间具有很强的化学键相互作用，有利于锂离子传输，可提升电池的倍率性能；同时该硼酸酯带有-(CH 2CH 2O) n-CO-CR 0＝CH 2结构，采用该硅基负极材料制备的负极片，在极片高温烘烤的过程中会发生交联反应使得硅基负极材料颗粒之间形成交联，有效保证硅负极极片在循环过程中的结构完整性，从而提升电池的循环性能。

Description

一种硅基负极材料及其制备方法和应用
本申请要求于2019年08月07日提交中国专利局、申请号为201910727508.4、申请名称为“一种硅基负极材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及锂离子电池技术领域，尤其涉及一种硅基负极材料及其制备方法和应用。
背景技术
锂离子电池具有能量密度高、循环寿命长以及环境友好的特点，已广泛应用于移动通信设备、笔记本电脑、数码相机等电子产品中，并逐渐在电动交通工具以及储能领域发挥作用。负极材料是锂离子电池的关键材料之一，目前应用最多的商业化锂离子电池负极材料是石墨，其理论比容量为372mAh/g，已不能满足高能量密度锂离子电池的要求。硅基负极材料的理论比容量可达到4200mAh/g，替代石墨负极可以显著提升电池能量密度，是非常有应用前景的下一代负极材料。
然而硅基材料在脱嵌锂的过程中会发生巨大的体积变化，导致循环性能差以及首次充放电效率低。目前的解决思路主要是硅基材料纳米化，以及将硅基材料与碳基材料复合，对硅基材料性能有一定的改善作用。但目前的硅基材料的性能仍然有待进一步提高。
发明内容
为了改善现有技术的不足，本申请的目的是提供一种硅基负极材料及其制备方法和应用，所述硅基负极材料可改善硅基材料的循环性能、首次充放电效率和锂离子传导性能，从而改善锂离子电池的循环寿命，提高锂离子电池的能量密度，并提高锂离子电池的倍率性能。
为了实现上述目的，本申请采取如下的技术解决方案：
本申请提供一种硅基负极材料，其中，所述硅基负极材料具有核壳结构，在壳层的外表面上接枝有硼酸酯；形成所述核的材料包括硅粉体和/或氧化亚硅粉体，形成所述壳的材料包括硼酸锂。
根据本申请，所述硼酸酯占所述硅基负极材料的重量百分比为0.01-2wt％。
根据本申请，核体的平均粒径为1nm-10μm。
根据本申请，所述的壳层的厚度为0.1-100nm。
根据本申请，所述的硼酸酯选自具有式(1)所示结构的化合物的一种或多种：
Figure PCTCN2020107849-appb-000001
其中，n为0-10000之间的整数，R 1和R 2相同或不同，彼此独立地选自H、烷基、烷氧基、烯基、烯氧基、芳基、芳氧基、-COCR 0＝CH 2、-OCOCR 0＝CH 2、-O(CH 2CH 2O) y1COCR 0＝CH 2(y1为大于等于0的整数)、-O(CH 2CH 2O) y2R 0(y2为大于等于1的整数)、-(CH 2CH 2O) y3R 0(y3为大于等于1的整数)、-(CH 2CH 2O) y4COCR 0＝CH 2(y4为大于等于0的整数)；
R 0选自H、烷基、芳基或一个或多个F取代的芳基；
其中，n、y1、y2、y3、y4分别代表相应重复单元的平均聚合度。
优选地，R 1和R 2相同或不同，彼此独立地选自C 1-6烷基、-OC 1-6烷基、C 2-6烯基、-OC 2-6烯基、-C 6H 5、-OC 6H 5、-COCH＝CH 2、-OCOCR 0＝CH 2、-O(CH 2CH 2O) y1COCR 0＝CH 2(y1为0-10之间的整数)、-O(CH 2CH 2O) y2R 0(y2为1-8之间的整数)、-(CH 2CH 2O) y3R 0(y3为1-5之间的整数)、-(CH 2CH 2O) y4COCR0＝CH 2(y4为0-5之间的整数)；其中，R 0定义如上所述。
优选地，R 0选自H、C 1-6烷基、-C 6H 5或一个或多个F取代的-C 6H 5。
本申请中，所述硼酸酯中的R 1和R 2基团会发生部分水解，B原子会键合在无机硼酸锂表面，从而接枝在硼酸锂表面，制备得到所述硅基负极材料。
本申请单独使用或用作后缀或前缀的“烷基”意在包括具有1至20个，优选1-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的直链或支链饱和脂族烃基。例如，“C 1-6烷基”表示具有1、2、3、4、5或6个碳 原子的直链或支链烷基，“C 2-4烷基”表示具有2、3或4个碳原子的直链或支链烷基。烷基的实例包括但不限于甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基和正己基。
本申请单独使用或用作后缀或前缀的“烯基”意在包括具有2至20个，优选2-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的包含烯基的直链或支链脂族烃基。例如，“C 2-6烯基”表示具有2、3、4、5或6个碳原子的烯基。烯基的实例包括但不限于乙烯基、烯丙基、1-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、2-甲基丁-2-烯基、3-甲基丁-1-烯基、1-戊烯基、3-戊烯基和4-己烯基。
本申请使用的术语“芳基”指由5至20个碳原子构成的芳族环结构。例如：包含5、6、7和8个碳原子的芳族环结构，可以是单环芳族基团，例如苯基；包含8、9、10、11、12、13或14个碳原子的环结构，可以是多环的，例如萘基、蒽基、菲基。术语“芳基”还包括具有两个或更多个环的多环环系，其中两个或更多个碳为两个相邻环所共有(所述环为“稠环”)，其中至少一个环是芳族的且其它环例如可以是环烷基、环烯基、环炔基、芳基和/或杂环基。多环的实例包括但不限于2,3-二氢-1,4-苯并二氧杂环己二烯和2,3-二氢-1-苯并呋喃。
本申请使用的术语“烷氧基”中的“烷基”的定义同前。
本申请使用的术语“芳氧基”中的“芳基”的定义同前。
根据本申请，所述的硅基负极材料的比表面积为0.5～1000m 2/g。
本申请还提供一种上述硅基负极材料的制备方法，包括如下步骤：
1)将硅粉体和/或氧化亚硅粉体与硼酸锂粉体混合，惰性气氛保护下煅烧，得到具有核壳结构的材料，形成所述核的材料包括硅粉体和/或氧化亚硅粉体，形成所述壳的材料包括硼酸锂；
2)将步骤1)的具有核壳结构的材料与硼酸酯、有机溶剂和水混合，反应，制备得到所述硅基负极材料。
根据本申请，步骤1)中，所述混合例如在球磨机中进行，所述混合的时间为2～24h。
根据本申请，步骤1)中，所述煅烧的温度为800～1000℃，所述煅烧的时间为0.1～12h。所述煅烧过程中，硼酸锂粉体在高温下融化后包覆在硅粉 体和/或氧化亚硅粉体表面，得到具有核壳结构的材料。
根据本申请，步骤1)中，所述硅粉体和/或氧化亚硅粉体与硼酸锂的质量比(95-99.9)：(0.1-5)。
根据本申请，步骤1)中，所述惰性气氛是指不与反应体系发生反应的气氛，例如可以是氮气、惰性气体等。
根据本申请，步骤2)中，所述有机溶剂选自乙醇、丙酮、甲苯和二甲苯中的至少一种。
根据本申请，步骤2)中，所述反应的温度为20～100℃，所述反应的时间为0.1～24h；所述反应例如在搅拌条件下进行。
根据本申请，步骤2)中，硼酸酯、有机溶剂和水的质量比为(0.1～99.8％)：(0.1～99.8％)：(0.1～99.8％)。
根据本申请，步骤2)中，步骤1)的具有核壳结构的材料与硼酸酯的质量比为(1～80)：(99～20)；制备得到的最终产品中，硼酸酯的含量占0.01-2wt％。
本申请中，反应过程中硼酸酯会接枝在壳层表面，当壳层表面全部接枝硼酸酯后，无法进行更多的接枝反应，此时，最终产品中的硼酸酯的含量取决于硼酸酯的分子量，硼酸酯分子量越大，最终产品中硼酸酯质量占比越大。
根据本申请，所述方法还包括后处理步骤：对反应结束后的混合体系进行过滤或离心除去液体，用有机溶剂或水洗涤，干燥。
根据本申请，所述方法具体包括如下步骤：
S1：将硅粉体和/或氧化亚硅粉体与硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨2～24h，然后在惰性气氛保护下800～1000℃煅烧0.1～12h，得到具有核壳结构的材料，形成所述核的材料包括硅粉体和/或氧化亚硅粉体，形成所述壳的材料包括硼酸锂；
S2：将硼酸酯、有机溶剂与水混合均匀形成混合溶液；再将具有核壳结构的材料加入混合溶液中，保持20～100℃，搅拌0.1～24h，过滤或离心除去液体，用有机溶剂或水洗涤，干燥，可得所述硅基负极材料。
本申请还提供一种硅基负极材料，所述硅基负极材料是通过上述方法制备得到的。
本申请还提供上述硅基负极材料在液态锂离子电池或凝胶态锂离子电池或固态锂离子电池中的应用。
本申请还提供一种液态锂离子电池，所述液态锂离子电池包括正极极片、负极极片、隔膜和电解液，其中，所述负极极片采用上述的硅基负极材料制备得到。
本申请还提供一种凝胶态锂离子电池，所述凝胶态锂离子电池包括正极极片、负极极片和凝胶态电解质膜，其中，所述负极极片采用上述的硅基负极材料制备得到。
本申请还提供一种固态锂离子电池，所述固态锂离子电池包括正极极片、负极极片和固态电解质膜，其中，所述负极极片采用上述的硅基负极材料制备得到。
本申请的有益效果：
本申请提供了一种硅基负极材料及其制备方法和应用，所述硅基负极材料表面具有硼酸锂包覆层，包覆层可以有效减弱负极表面副反应，提高材料的首次充放电效率；硼酸锂包覆层与具有特定结构的硼酸酯之间具有很强的化学键相互作用，有利于锂离子传输，可提升电池的倍率性能；同时该硼酸酯带有-(CH 2CH 2O) n-CO-CR 0＝CH 2结构，采用该硅基负极材料制备的负极片，在极片高温烘烤的过程中会发生交联反应使得硅基负极材料颗粒之间形成交联，有效保证硅负极极片在循环过程中的结构完整性，从而提升电池的循环性能。
附图说明
图1为硅基负极材料结构示意图。
具体实施方式
下文将结合具体实施例对本申请的制备方法做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本申请，而不应被解释为对本申请保护范围的限制。凡基于本申请上述内容所实现的技术均涵盖在本申请旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
下述实施例中所使用的硼酸酯B1～B8的定义如下表1所示：
表1
硼酸酯 n R 1 R 2 R 0
B1 3 -OCH 3 -O(CH 2CH 2O) 10COCH＝CH 2 -H
B2 8 -C 2H 5 -(CH 2CH 2O) 5COC(C 2H 5)＝CH 2 -CH 3
B3 15 -CH 2CH＝CH 3 -O(CH 2CH 2O) 8CH 3 -C 6H 5
B4 20 -OCH 2CH 2CH＝CH 3 -(CH 2CH 2O) 3C 2H 5 -C 2H 5
B5 58 -C 6H 5 -OCH 3 -C 3H 7
B6 128 -OC 6H 5 -OC 6H 5 -C 6F 5
B7 450 -COCH＝CH 2 -C 4H 9 -C 6H 4F
B8 950 -OCOC(CH 3)＝CH 2 -COCH＝CH 2 -C 4H 9
实施例1
将99.9份(质量份，同下)平均粒径为1nm的硅粉体与0.1份硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨2h，然后在惰性气氛保护下1000℃煅烧0.1h，即可得到具有核壳结构的材料(记作M1)，形成所述核的材料包括硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为0.1nm。
再将硼酸酯B1、甲苯与水混合均匀形成混合溶液，其中水占混合溶液质量分数为0.1％，甲苯占混合溶液质量分数为0.1％，硼酸酯B1占混合溶液质量分数为99.8％；再将1份质量的M1加入99份质量的上述混合溶液中，保持100℃，搅拌24h，过滤除去液体，用甲苯洗涤，干燥，可得本申请的硅基负极材料。
用所得硅基负极材料搭配钴酸锂正极、聚乙烯隔膜和锂离子电池常规商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例1a
用平均粒径为1nm的硅粉体制备成负极，搭配钴酸锂正极、聚乙烯隔膜和锂离子电池常规商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例1b
用实施例1中的M1制备成负极，搭配钴酸锂正极、聚乙烯隔膜和锂离子电池常规商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
实施例2
将95份平均粒径为10μm的氧化亚硅粉体与5份硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨24h，然后在惰性气氛保护下800℃煅烧12h，即可得到具有核壳结构的材料(记作M2)，形成所述核的材料包括氧化亚硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为100nm。
再将硼酸酯B2、丙酮与水混合均匀形成混合溶液，其中水占混合溶液质量分数为99.8％，丙酮占混合溶液质量分数为0.1％，硼酸酯B2占混合溶液质量分数为0.1％；再将10份质量的M2加入90份质量的上述混合溶液中，保持20℃，搅拌0.1h，离心除去液体，用水洗涤，干燥，可得本申请的硅基负极材料。
用所得硅基负极材料搭配磷酸铁锂正极、聚乙烯陶瓷复合隔膜和锂离子电池常规商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例2a
用平均粒径为10μm的氧化亚硅粉体制备成负极，搭配磷酸铁锂正极、聚乙烯陶瓷复合隔膜和锂离子电池常规商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例2b
用实施例2中的M2制备成负极，搭配磷酸铁锂正极、聚乙烯陶瓷复合隔膜和锂离子电池常规商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
实施例3
将98份平均粒径为1μm的氧化亚硅粉体与2份硼酸锂粉体混合均匀得到 混合粉体，将混合粉体用球磨机球磨4h，然后在惰性气氛保护下900℃煅烧6h，即可得到具有核壳结构的材料(记作M3)，形成所述核的材料包括氧化亚硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为15nm。
再将硼酸酯B3、乙醇与水混合均匀形成混合溶液，其中水占混合溶液质量分数为50％，乙醇占混合溶液质量分数为48％，硼酸酯B3占混合溶液质量分数为2％；再将50份质量的M3加入50份质量的上述混合溶液中，保持50℃，搅拌1h，过滤除去液体，用乙醇洗涤，干燥，可得本申请的硅基负极材料。
用所得硅基负极材料搭配镍钴锰三元(NCM622)正极和PVDF凝胶态电解质膜组装成凝胶态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例3a
用平均粒径为1μm的氧化亚硅粉体制备成负极，搭配镍钴锰(NCM622)三元正极和PVDF凝胶态电解质膜组装成凝胶态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例3b
用实施例3中的M3制备成负极，搭配镍钴锰(NCM622)三元正极和PVDF凝胶态电解质膜组装成凝胶态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
实施例4
将99份平均粒径为50nm的硅粉体与1份硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨6h，然后在惰性气氛保护下850℃煅烧8h，即可得到具有核壳结构的材料(记作M4)，形成所述核的材料包括硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为3nm。
再将硼酸酯B4、二甲苯与水混合均匀形成混合溶液，其中水占混合溶液质量分数为98％，二甲苯占混合溶液质量分数为0.5％，硼酸酯B4占混合溶液质量分数为1.5％；再将40份质量的M4加入60份质量的上述混合溶液中，保持30℃，搅拌0.5h，过滤除去液体，用乙醇洗涤，干燥，可得本申请的硅基负 极材料。
用所得硅基负极材料搭配镍钴锰三元正极和硫化物固态电解质膜组装成固态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例4a
用平均粒径为50nm的硅粉体制备成负极，搭配镍钴锰三元正极和硫化物固态电解质膜组装成固态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例4b
用实施例4中的M4制备成负极，搭配镍钴锰三元正极和硫化物固态电解质膜组装成固态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
实施例5
将98.5份平均粒径为500nm的氧化亚硅粉体与1.5份硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨5h，然后在惰性气氛保护下920℃煅烧1.5h，即可得到具有核壳结构的材料(记作M5)，形成所述核的材料包括氧化亚硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为2.5nm。
再将硼酸酯B5、硼酸酯B6、乙醇与水混合均匀形成混合溶液，其中水占混合溶液质量分数为20％，乙醇占混合溶液质量分数为75％，硼酸酯B5占混合溶液质量分数为5％，硼酸酯B6占混合溶液质量分数为5％；再将80份质量的M5加入20份质量的上述混合溶液中，保持50℃，搅拌3h，过滤除去液体，用乙醇/水混合溶剂洗涤，干燥，可得本申请的硅基负极材料。
用所得硅基负极材料搭配镍钴锰三元正极和硫化物固态电解质膜组装成固态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例5a
用平均粒径为500nm的氧化亚硅粉体制备成负极，搭配镍钴锰三元正极和硫化物固态电解质膜组装成固态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例5b
用实施例5中的M5制备成负极，搭配镍钴锰三元正极和硫化物固态电解质膜组装成固态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
实施例6
将99.5份平均粒径为5nm的硅粉体与0.5份硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨3.5h，然后在惰性气氛保护下820℃煅烧1h，即可得到具有核壳结构的材料(记作M6)，形成所述核的材料包括硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为0.5nm。
再将硼酸酯B7、硼酸酯B8、乙醇与水混合均匀形成混合溶液，其中水占混合溶液质量分数为10％，乙醇占混合溶液质量分数为77％，硼酸酯B7占混合溶液质量分数为10％，硼酸酯B8占混合溶液质量分数为3％；再将60份质量的M6加入40份质量的上述混合溶液中，保持70℃，搅拌1h，过滤除去液体，用乙醇洗涤，干燥，可得本申请的硅基负极材料。
用所得硅基负极材料搭配钴酸锂正极和PVDF凝胶态电解质膜组装成凝胶态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例6a
用平均粒径为5nm的硅粉体制备成负极，搭配钴酸锂正极和PVDF凝胶态电解质膜组装成凝胶态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例6b
用实施例6中的M6制备成负极，搭配钴酸锂正极和PVDF凝胶态电解质膜 组装成凝胶态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
实施例7
将99.2份平均粒径为100nm的氧化亚硅粉体与0.8份硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨11h，然后在惰性气氛保护下880℃煅烧1.5h，即可得到具有核壳结构的材料(记作M7)，形成所述核的材料包括氧化亚硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为2nm。
再将硼酸酯B1、硼酸酯B3、硼酸酯B6、乙醇与水混合均匀形成混合溶液，其中水占混合溶液质量分数为50％，乙醇占混合溶液质量分数为44％，硼酸酯B1占混合溶液质量分数为2％，硼酸酯B3占混合溶液质量分数为2％；硼酸酯B6占混合溶液质量分数为2％；再将50份质量的M7加入50份质量的上述混合溶液中，保持45℃，搅拌5h，过滤除去液体，用乙醇洗涤，干燥，可得本申请的硅基负极材料。
用所得硅基负极材料搭配磷酸铁锂正极、聚丙烯PP/聚乙烯PE/聚丙烯PP三层复合隔膜和常规的锂离子电池商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例7a
用平均粒径为100nm的氧化亚硅粉体制备成负极，搭配磷酸铁锂正极、聚丙烯PP/聚乙烯PE/聚丙烯PP三层复合隔膜和常规的锂离子电池商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例7b
用实施例7中的M7制备成负极，搭配磷酸铁锂正极、聚丙烯PP/聚乙烯PE/聚丙烯PP三层复合隔膜和常规的锂离子电池商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
实施例8
将97.8份平均粒径为20nm的硅粉体与2.2份硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨4h，然后在惰性气氛保护下840℃煅烧2.5h，即可得到具有核壳结构的材料(记作M8)，形成所述核的材料包括硅粉体，形成所述壳的材料包括硼酸锂，其中壳层厚度为8nm。
再将硼酸酯B2、硼酸酯B5、硼酸酯B8、丙酮与水混合均匀形成混合溶液，其中水占混合溶液质量分数为2％，丙酮占混合溶液质量分数为76％，硼酸酯B2占混合溶液质量分数为5％，硼酸酯B5占混合溶液质量分数为10％；硼酸酯B8占混合溶液质量分数为7％；再将50份质量的M8加入50份质量的上述混合溶液中，保持65℃，搅拌2h，过滤除去液体，用水洗涤，干燥，可得本申请的硅基负极材料。
用所得硅基负极材料搭配镍钴锰三元(NCM523)正极、聚乙烯陶瓷涂层复合隔膜和常规的锂离子电池商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例8a
用平均粒径为20nm的硅粉体制备成负极，搭配镍钴锰三元(NCM523)正极、聚乙烯陶瓷涂层复合隔膜和常规的锂离子电池商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
对比例8b
用实施例8中的M8制备成负极，搭配镍钴锰三元(NCM523)正极、聚乙烯陶瓷涂层复合隔膜和常规的锂离子电池商业电解液组装成液态锂离子电池，测试其倍率性能(测试方法：测试3C倍率下放电容量保持率)，测试其在25℃、1C/1C充放电条件下的循环性能，测试其首次充放电效率和能量密度。
表2 实施例1-8和对比例1a-8b组装得到的电池的性能
Figure PCTCN2020107849-appb-000002
Figure PCTCN2020107849-appb-000003
从表2可以看出，采用本申请方法制备的硅基负极材料制得的锂离子电池，首次放电效率、能量密度、循环寿命及倍率性能均得到了明显改善。
具体地，所述硅基负极材料表面具有硼酸锂包覆层，包覆层可以有效减弱负极表面副反应，提高材料的首次充放电效率；硼酸锂包覆层与具有特定结构的硼酸酯之间具有很强的化学键相互作用，有利于锂离子传输，可提升电池的倍率性能；同时该硼酸酯带有-(CH 2CH 2O) n-CO-CR 0＝CH 2结构，采用该硅基负极材料制备的负极片，在极片高温烘烤的过程中会发生交联反应使得硅基负极材料颗粒之间形成交联，有效保证硅负极极片在循环过程中的结构完整性，从而提升电池的循环性能。
以上，对本申请的实施方式进行了说明。但是，本申请不限定于上述实施方式。凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (22)

  1. 一种硅基负极材料，其中，所述硅基负极材料具有核壳结构，在壳层的外表面上接枝有硼酸酯；形成所述核的材料包括硅粉体和/或氧化亚硅粉体，形成所述壳的材料包括硼酸锂。
  2. 根据权利要求1所述的硅基负极材料，其中，所述硼酸酯占所述硅基负极材料的重量百分比为0.01-2wt％。
  3. 根据权利要求1或2所述的硅基负极材料，其中，核体的平均粒径为1nm-10μm。
  4. 根据权利要求1-3任一项所述的硅基负极材料，其中，所述壳层的厚度为0.1-100nm。
  5. 根据权利要求1-4任一项所述的硅基负极材料，其中，所述的硼酸酯选自具有式(1)所示结构的化合物的一种或多种：
    Figure PCTCN2020107849-appb-100001
    在式(1)中，n为0-10000之间的整数，R 1和R 2独立地选自H、烷基、烷氧基、烯基、烯氧基、芳基、芳氧基、-COCR 0＝CH 2、-OCOCR 0＝CH 2、-O(CH 2CH 2O) y1COCR 0＝CH 2、-O(CH 2CH 2O) y2R 0、-(CH 2CH 2O) y3R 0、-(CH 2CH 2O) y4COCR 0＝CH 2；其中，y1为大于等于0的整数、y2为大于等于1的整数、y3为大于等于1的整数、y4为大于等于0的整数；
    R 0选自H、烷基、芳基或一个或多个F取代的芳基；
    其中，n、y1、y2、y3、y4分别代表相应重复单元的平均聚合度。
  6. 根据权利要求5所述的硅基负极材料，其中，R 1和R 2独立地选自C 1-6烷基、-OC 1-6烷基、C 2-6烯基、-OC 2-6烯基、-C 6H 5、-OC 6H 5、-COCH＝CH 2、-OCOCR 0＝CH 2、-O(CH 2CH 2O) y1COCR 0＝CH 2、-O(CH 2CH 2O) y2R 0、-(CH 2CH 2O) y3R 0、-(CH 2CH 2O) y4COCR 0＝CH 2；其中，y1为0-10之间的整数、y2为1-8之间的整数、y3为1-5之间的整数、y4为0-5之间的整数。
  7. 根据权利要求5或6所述的硅基负极材料，其中，R 0选自H、C 1-6烷基、-C 6H 5或一个或多个F取代的-C 6H 5。
  8. 一种权利要求1-7任一项所述硅基负极材料的制备方法，其中，包括 如下步骤：
    1)将硅粉体和/或氧化亚硅粉体与硼酸锂粉体混合，惰性气氛保护下煅烧，得到具有核壳结构的材料，形成所述核的材料包括硅粉体和/或氧化亚硅粉体，形成所述壳的材料包括硼酸锂；
    2)将步骤1)的具有核壳结构的材料与硼酸酯、有机溶剂和水混合，反应，制备得到所述硅基负极材料。
  9. 根据权利要求8所述的制备方法，其中，步骤1)中，所述混合例如在球磨机中进行，所述混合的时间为2～24h。
  10. 根据权利要求8所述的制备方法，其中，步骤1)中，所述煅烧的温度为800～1000℃，所述煅烧的时间为0.1～12h。
  11. 根据权利要求8所述的制备方法，其中，步骤1)中，所述硅粉体和/或氧化亚硅粉体与硼酸锂的质量比为(95-99.9)：(0.1-5)。
  12. 根据权利要求8所述的制备方法，其中，步骤2)中，所述有机溶剂选自乙醇、丙酮、甲苯和二甲苯中的至少一种。
  13. 根据权利要求8所述的制备方法，其中，步骤2)中，所述反应的温度为20～100℃，所述反应的时间为0.1～24h；所述反应例如在搅拌条件下进行。
  14. 根据权利要求8所述的制备方法，其中，步骤2)中，硼酸酯、有机溶剂和水的质量比为(0.1～99.8％)：(0.1～99.8％)：(0.1～99.8％)。
  15. 根据权利要求8所述的制备方法，其中，步骤2)中，步骤1)的具有核壳结构的材料与硼酸酯的质量比为(1～80)：(99～20)。
  16. 根据权利要求8所述的制备方法，其中，所述方法还包括后处理步骤：对反应结束后的混合体系进行过滤或离心除去液体，用有机溶剂或水洗涤，干燥。
  17. 根据权利要求8-16任一项所述的制备方法，其中，所述方法具体包括如下步骤：
    S1：将硅粉体和/或氧化亚硅粉体与硼酸锂粉体混合均匀得到混合粉体，将混合粉体用球磨机球磨2～24h，然后在惰性气氛保护下800～1000℃煅烧0.1～12h，得到具有核壳结构的材料，形成所述核的材料包括硅粉体和/或氧化亚硅粉体，形成所述壳的材料包括硼酸锂；
    S2：将硼酸酯、有机溶剂与水混合均匀形成混合溶液；再将具有核壳结构的材料加入混合溶液中，保持20～100℃，搅拌0.1～24h，过滤或离心除去液体，用有机溶剂或水洗涤，干燥，可得所述硅基负极材料。
  18. 一种硅基负极材料，所述硅基负极材料是通过权利要求8-17任一项所述方法制备得到的。
  19. 权利要求1-7或18任一种所述的硅基负极材料在液态锂离子电池或凝胶态锂离子电池或固态锂离子电池中的应用。
  20. 一种液态锂离子电池，所述液态锂离子电池包括正极极片、负极极片、隔膜和电解液，其中，所述负极极片采用权利要求1-7或18任一种所述的硅基负极材料制备得到。
  21. 一种凝胶态锂离子电池，所述凝胶态锂离子电池包括正极极片、负极极片和凝胶态电解质膜，其中，所述负极极片采用权利要求1-7或18任一种所述的硅基负极材料制备得到。
  22. 一种固态锂离子电池，所述固态锂离子电池包括正极极片、负极极片和固态电解质膜，其中，所述负极极片采用权利要求1-7或18任一种所述的硅基负极材料制备得到。
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