WO2023134366A1 - 硅碳负极材料及其制备方法和应用 - Google Patents

硅碳负极材料及其制备方法和应用 Download PDF

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WO2023134366A1
WO2023134366A1 PCT/CN2022/138579 CN2022138579W WO2023134366A1 WO 2023134366 A1 WO2023134366 A1 WO 2023134366A1 CN 2022138579 W CN2022138579 W CN 2022138579W WO 2023134366 A1 WO2023134366 A1 WO 2023134366A1
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silicon
negative electrode
electrode material
carbon negative
material according
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French (fr)
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钟应声
余海军
李爱霞
谢英豪
李波
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Priority to ES202490005A priority Critical patent/ES2994592B2/es
Priority to GB2314846.3A priority patent/GB2619868A/en
Publication of WO2023134366A1 publication Critical patent/WO2023134366A1/zh
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    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
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    • 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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    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the embodiments of the present application relate to the technical field of lithium-ion batteries, such as silicon-carbon negative electrode materials and their preparation methods and applications.
  • the new energy automobile industry has higher requirements on the power density and service life of the power battery, and the anode material with excellent lithium storage performance and environmental friendliness in the power battery is very important, compared with graphite (carbon-based) anode materials .
  • Silicon-based anode materials have extremely high theoretical specific capacity.
  • the volume expansion of silicon will cause the electrode material to detach from the current collector, and even cause the powdering of silicon itself, and the function of the negative electrode material will fail.
  • silicon itself has poor conductivity, which reduces the transmission efficiency of the battery.
  • the volume expansion of silicon will reduce the pores inside the battery, and metal lithium will be precipitated, which poses a serious safety problem.
  • the R is at least one of zirconium, copper, nickel, cobalt, manganese, chromium, titanium, molybdenum and silver.
  • the Z a O b is one of Al 2 O 3 , MgO and ZnO.
  • the silicon-carbon negative electrode material is Li 0.04 - Si@C-CuO/B-MgO, Li 0.03 - Si@C-MnO/B-MgO, Li 0.02 - Si@C-ZrO 2 /B-Al 2 At least one of O 3 , Li 0.02 - Si@C-NiO/B-Al 2 O 3 .
  • the graphite block is prepared by the following method: recycle, pyrolyze and sieve the power battery to obtain battery black powder, add sulfuric acid to adjust the pH, add a reducing agent to stir, separate solid and liquid, take the solid phase and wash it with water, and then A dispersant is added for mixing, pulverized, and pressed to form a graphite block.
  • the reducing agent is at least one of sodium pyrosulfate, potassium pyrosulfate, sodium sulfite, potassium sulfite, sodium thiosulfate, and potassium thiosulfate.
  • the solid-to-liquid ratio of the reducing agent and sulfuric acid is 10-100 g/L.
  • the dispersant is at least one of protein solution, glycerin, and benzoic acid.
  • the particle size of the graphite powder is ⁇ 5 ⁇ m.
  • the solid-to-liquid ratio of the silica sol, graphite, and boric acid polymer is (10-50) g: (2-30) g: (0.1-5) ml.
  • the active metal Z is at least one of magnesium, aluminum, manganese and zinc.
  • the lithium ion conductor membrane is characterized in that only lithium ions can pass through during electrolysis.
  • the conductive agent is mixed with dimethyl glycol, ethylene carbonate, and lithium hexafluorophosphate in a volume ratio of 1:1.5:1.
  • the anode half-cell electrolyte is a lithium silicate solution, and the concentration of the lithium silicate solution is 0.02-0.15mol/L.
  • the lithium silicate is at least one of Li 2 Si 5 O 11 , Li 8 SiO 6 , Li 2 SiO 3 , Li 4 SiO 4 , Li 6 Si 2 O 7 , and Li 2 Si 2 O 5 .
  • the mass ratio of the solid phase, Li f -Si@CR s O t /B is (0.1-5):100.
  • the lithium intercalation treatment can be expressed as follows:
  • the heat treatment temperature is 200-400° C.
  • the heat treatment time is 2-6 hours.
  • the present application also provides a battery, including the silicon-carbon negative electrode material.
  • Fig. 3 is a specific capacity diagram of the first to 100th discharges of Examples 1 and 3 of the present application and Comparative Examples 1 and 2.
  • the silicon carbon negative electrode material of this embodiment has a chemical formula of Li 0.02 - Si@C-ZrO 2 /B-Al 2 O 3 .
  • the electrode in the cathode half-cell is cathode graphite, and the graphite is attached with 10g of Si@C-ZrO 2 /B material.
  • 400ml conductive agent dimethyl ethylene glycol: ethylene carbonate: 1.5M lithium hexafluorophosphate mixed according to the volume ratio of 1:1.5:1
  • the electrode in the anode half tank is aluminum sheet
  • the electrolyte in the anode half tank is 400ml0.
  • the silicon carbon negative electrode material of this embodiment has a chemical formula of Li 0.02 -Si@C-NiO/B-Al 2 O 3 .
  • the electrode in the cathode half-cell is cathode graphite, and the graphite is attached with 10g of Si@C-NiO/B material, add 400ml Conductive agent (dimethyl ethylene glycol: ethylene carbonate: 1.5mol/L lithium hexafluorophosphate is mixed according to the volume ratio of 1:1.5:1), the electrode in the anode half tank is aluminum sheet, and the electrolyte in the anode half tank is 400ml.
  • the silicon carbon negative electrode material of this embodiment has a chemical formula of Li 0.03 -Si@C-MnO/B-MgO.
  • the electrode in the cathode half-cell is cathode graphite, and the graphite is attached with 10g of Si@C-NiO/B material, add 480ml Conductive agent (dimethyl ethylene glycol: ethylene carbonate: 1.5mol/L lithium hexafluorophosphate mixed according to the volume ratio of 1:1.5:1), the electrode in the anode half tank is aluminum sheet, and the electrolyte in the anode half tank is 480ml.
  • the silicon carbon negative electrode material of this embodiment has a chemical formula of Li 0.03 -Si@C-MnO/B-MgO.
  • the electrode in the cathode half-cell is cathode graphite, and the graphite is attached with 10g of Si@C-NiO/B material, add 480ml Conductive agent (dimethyl ethylene glycol: ethylene carbonate: 1.5mol/L lithium hexafluorophosphate mixed according to the volume ratio of 1:1.5:1), the electrode in the anode half tank is aluminum sheet, and the electrolyte in the anode half tank is 480ml.
  • the silicon-carbon anode material of this comparative example has a chemical formula of Li 0.02 - Si@C-ZrO 2 /B-Al 2 O 3 .
  • the silicon-carbon anode material of this comparative example has a chemical formula of Li 0.03 -Si@C-MnO/B-MgO.
  • the electrode in the cathode half-cell is cathode graphite, graphite is attached with 10g of Si@C-MnO/B material, add 480ml Conductive agent (dimethyl ethylene glycol: ethylene carbonate: 1.5mol/L lithium hexafluorophosphate mixed according to the volume ratio of 1:1.5:1), the electrode in the anode half tank is aluminum sheet, and the electrolyte in the anode half tank is 480ml.
  • Embodiment 1-4 and comparative example 1-2 analyze:
  • Figure 1 is the SEM image of the silicon-carbon negative electrode material of Comparative Example 2. It can be seen that the silicon-carbon negative electrode material Li 0.03 -Si@C-MnO-MgO prepared in Comparative Example 2 has many fast and flake shapes, and the size of the fast silicon-carbon negative electrode material is is about 5 ⁇ m, and the SEM image of the silicon-carbon negative electrode material in Figure 2 Example 3, it can be seen that the silicon-carbon negative electrode material Li 0.03 -Si@C-MnO/B-MgO prepared in Example 3 has many flakes and few fast shapes. The size of the flaky silicon carbon negative electrode material is about 400-800nm.
  • Table 1 shows the specific surface area and D50 of the silicon-carbon negative electrode materials prepared in Examples 1-3 and Comparative Examples 1 and 2.
  • the specific surface area and D50 of the silicon-carbon negative electrode materials prepared in Examples 1-3 are better than those of Comparative Examples 1 and 2.
  • the specific surface area of the material, D50 is higher than that of the silicon-carbon negative electrode material in Comparative Example 2
  • the D50 of the silicon-carbon negative electrode material prepared in Comparative Example 1 is higher than that of the silicon-carbon negative electrode material in Comparative Example 2.
  • D50 indicating that the specific surface area of the silicon-carbon negative electrode material after adding boric acid polymer (BAP), D50 is better.
  • Embodiment 1,3 and comparative example 1,2 analyze:
  • the preparation of the electrode adopts an electrochemical method, first of all, the preparation of the pole piece: the silicon carbon negative electrode active material, Super P conductive agent, and binder prepared in Example 1, Example 3, and Comparative Examples 1 and 2, according to 8: 1.5:0.5 mass ratio, weighed with an electronic balance, placed in a specific weighing bottle, dispersed evenly, using ultra-pure water as a solvent, using a magnetic stirrer to mix the slurry, and then passing the prepared slurry through the coating The cloth machine is used for coating, and the current collector is made of copper foil, which is placed in an oven at 85°C for 8 hours. Finally, slice it with a microtome to obtain a pole piece with a diameter of about 12 mm that can be used for electrochemical testing.
  • Button battery assembly Calculate the active material load of the pole piece, transfer the pole piece to the glove box, prepare to stack the electrode shell, silicon negative electrode, diaphragm, metal lithium counter electrode, and foamed nickel in order, and then charge the button Assemble. After the half-cells are assembled, they are pressure-packed. After packaging, the button cell needs to be left overnight at room temperature. During the test, keep the test environment at room temperature (15-25°C), the voltage range is 0.001-1.5V, the current density is set to 0.5A/g, 1A/g, 1.5A/g, 3A/g, and the number of cycles is 100 times. See Figure 3.
  • Figure 3 The specific capacity diagrams of the first to 100th discharges of Examples 1 and 3 and Comparative Examples 1 and 2, combined with Table 1 and Figure 3, at a current density of 0.5A/g, the first discharge specific capacities of Examples 1 and 3 respectively Reached 2259mAh/g, 2647mAh/g, comparative examples 1 and 2 first discharge specific capacity respectively reached 1798mAh/g, 2302mAh/g, under the current density of 3A/g, when the number of cycles reached 31 times, the discharge of examples 1 and 3 The specific capacity reaches 1473mAh/g and 1289mAh/g, and the discharge specific capacity of comparative examples 1 and 2 is 601mAh/g and 1018mAh/g at the 31st time, and examples 1 and 3 show excellent rate and cycle performance.
  • the specific surface area, D 50 , and D 90 of the silicon-carbon negative electrode prepared in Examples 1 and 3 are better than those prepared in Comparative Example 1-2, especially the specific surface area, D 50 , and D 90 of the silicon-carbon negative electrode prepared in Comparative Example 2.
  • the specific surface area, D 50 , and D 90 of the silicon-carbon negative electrode prepared in Ratio 1 are higher than the specific surface area, D 50 , and D 90 of the silicon-carbon negative electrode prepared in Ratio 1, indicating that the performance of the silicon-carbon negative electrode treated with boric acid polymer (BAP) is better.

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Abstract

本申请属于锂离子电池技术领域，公布了硅碳负极材料及其制备方法和应用，该硅碳负极材料的化学通式为Li f -Si@C-R sO t/B-Z aO b；R为锆、铜、镍、钴、锰、铬、钛、钼、银、镁、钙、锗、锡、锑中至少一种；Z为铝、镁、锌中的至少一种，其中s、t分别独立的为1、2、3、4或5，a＝1或2，b＝1或3。本申请的硅碳负极材料由于含有BAP(硼酸的高聚合物)，使得硅碳负极材料的比表面积、D50更佳，进而提升了电化学性能。

Description

硅碳负极材料及其制备方法和应用 技术领域
本申请实施例涉及锂离子电池技术领域，例如硅碳负极材料及其制备方法和应用。
背景技术
近年来，因为废动力电池中存在的某些金属和电解质的释放对环境有害，也基于锂离子电池资源有限的原因，相关回收企业加大了对废动力电池回收。废动力电池中常见的可回收材料是锂钴氧化物、磷酸铁锂和钴镍锰氧化物等正极材料、铜铝箔等集电体材料、以及石墨等负极材料。其中石墨是一种关键的负极材料，因此开发从报废动力电池中回收石墨的高效回收再利用工艺变得非常重要，可以减少采矿对环境的影响、提高石墨资源循环利用率。
新能源汽车产业对的动力电池功率密度、使用寿命的要求原来越高，而动力电池中储锂性能优异而又对环境友好的负极材料至关重要，相对于石墨(碳基)负极材料来说，硅基负极材料具有极高的理论比容量。目前，硅基负极材料在脱嵌锂的过程中，硅的体积膨胀会导致电极材料从集电体上脱离，甚至造成硅本身的粉化，负极材料功能失效。此外，硅本身导电性较差，降低电池的传输效率，硅的体积膨胀会使电池内部的孔隙变少，金属锂析出，存在着严重的安全性问题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提出一种硅碳负极材料及其制备方法和应用，该硅碳负极材料解决了硅负极的体积变化大、材料结构的破坏、负极的功能失效等问题，同时实现废旧动力电池中石墨废料回收，并提高在负极材料方面的高效利用价值。
本申请实施例中提供以下技术方案：
一种硅碳负极材料，其化学通式为Li f -Si@C-R sO t/B-Z aO b；所述R为锆、铜、镍、钴、锰、铬、钛、钼、银、镁、钙、锗、锡、锑中至少一种；所述Z为铝、 镁、锌中的至少一种，其中s、t分别独立的为1、2、3、4或5，a＝1或2，b＝1或3。
优选地，所述R为锆、铜、镍、钴、锰、铬、钛、钼、银中至少一种。
优选地，所述Z aO b为Al 2O 3、MgO、ZnO中的一种。
优选地，所述R sO t为ZrO 2、NiO、MnO、CuO中的至少一种。
优选地，所述硅碳负极材料为Li 0.04 -Si@C-CuO/B-MgO、Li 0.03 -Si@C-MnO/B-MgO、Li 0.02 -Si@C-ZrO 2/B-Al 2O 3、Li 0.02 -Si@C-NiO/B-Al 2O 3中的至少一种。
一种硅碳负极材料的制备方法，所述的制备方法用于制备上述硅碳负极材料。
一种硅碳负极材料的制备方法，包括以下步骤：
将硅溶胶、可溶性R盐和硼酸聚合物混合搅拌，再加入石墨粉混合，反应，得到Si@C-R盐/BAP前体，热处理，得到Si@C-R sO t/B；
在石墨块为阴极、金属Z为阳极的电解槽中，用锂离子导体膜分隔电解槽为两个半槽，分别为阴极半槽和阳极半槽，将Si@C-R sO t/B置于阴极半槽通电电解，进行嵌锂处理，将阴极半槽固液分离，固体洗涤、烘干，得到Li f -Si@C-R sO t/B；
向阳极半槽中的电解液加入锂源搅拌，反应，固液分离，取固相与所述Li f -Si@C-R sO t/B混合均匀，再进行热处理，得到所述硅碳负极材料。
优选地，所述石墨块是由以下方法制备得到：将动力电池回收热解、筛分，得到电池黑粉，加硫酸调pH，并加入还原剂搅拌，固液分离，取固相水洗，再加入分散剂混合，粉碎，压制成型，得到石墨块。
进一步优选地，所述电池黑粉和硫酸的固液比为100-300g/L。
进一步优选地，所述硫酸的浓度为1-10mol/L；更优选地，硫酸的浓度为5-10mol/L。
优选地，所述还原剂为焦硫酸钠、焦硫酸钾、亚硫酸钠、亚硫酸钾、硫代硫酸钠、硫代硫酸钾中至少一种。
进一步优选地，所述还原剂和硫酸的固液比为10-100g/L。
进一步优选地，所述分散剂为蛋白液、甘油、苯甲酸中至少一种。
进一步优选地，所述固相和分散剂的固液比为30-400g/L。
进一步优选地，所述石墨粉的粒度<5μm。
优选地，所述硅溶胶、石墨、硼酸聚合物的固液比为(10-50)g：(2-30)g：(0.1-5)ml。
优选地，所述可溶性R盐中R的加入量为硅溶胶、石墨总质量的0.01-0.10。
优选地，所述可溶性R盐为锆、铜、镍、钴、锰、铬、钛、钼、银、镁钙、锗、锡、锑的可溶性的硫酸盐、硝酸盐、磷酸盐、氯化盐、溴化盐中至少一种。
优选地，所述硼酸聚合物为4-硼酸酯-4',4'-二甲基三苯胺、B,B'-噻吩[3,2-B]噻吩-2,5-二酰基双[硼酸]中的至少一种。
优选地，所述热处理的温度为200-400℃，热处理的时间为2-6h。
优选地，所述活性金属Z为镁、铝、锰、锌中的至少一种。
优选地，所述锂离子导体膜特点在于：电解时仅锂离子可以通过。
优选地，所述阴极半槽中由Si@C-R sO t/B材料、导电剂组成。
进一步优选地，所述导电剂是由二甲基乙二醇、碳酸乙烯酯、六氟磷酸锂按照1：1.5：1的体积比混合。
更优选地，所述六氟磷酸锂的浓度为1.5-2mol/L。
进一步优选地，所述阴极半槽中阴极电位附近附着为Si@C-R sO t/B材料。
进一步优选地，所述Si@C-R sO t/B材料、导电剂的固液比为10-50g/L。
优选地，所述控制阴极、阳极电势为阴极、阳极电势差>2.5V。
优选地，所述阳极半槽电解液为硅酸锂溶液，所述硅酸锂溶液的浓度为0.02-0.15mol/L。
进一步优选地，所述硅酸锂为Li 2Si 5O 11、Li 8SiO 6、Li 2SiO 3、Li 4SiO 4、Li 6Si 2O 7、Li 2Si 2O 5中的至少一种。
优选地，所述固相、Li f-Si@C-R sO t/B的质量比为(0.1-5)：100。
申请人研究利用硅酸锂当做嵌锂液中的电解液以及嵌锂处理的锂源进行嵌锂处理，嵌锂处理可由如下表示：
e·1/jLi jSi kO l+Si@C-R sO t/B+f·1/X·Z→Li f -Si@C-R sO t/B+f·1/X·Z X++(e-f) 1/jLi jSi kO l。
优选地，所述热处理的温度为200-400℃，热处理的时间为2-6h。
优选地，所述热处理的气氛为氮气。
本申请还提供一种电池，包括所述的硅碳负极材料。
相对于相关技术，本申请实施例的有益效果如下：
1、本申请实施例提供的硅碳负极材料由于含有Si@C-R sO t/B，使得硅碳负极材料的比表面积、D50更佳，进而提升了电化学性能。
2、本申请实施例在制备Si@C-R sO t/B中，通过硅溶胶、石墨粉与硼酸的高聚合物(BAP)共混，得到的稳定性能提高，其主要原因是BAP分子内含有N-B内配位键，硅溶胶、石墨粉与BAP共混复合得到Si@C-R sO t/B，热处理后，片状化更明显，块状结构较少，片状化结构表面积更大，受体积变化的影响较小，接触点位多，因此优化了离子扩散方式(图1-3的SEM图中，相较于对比例)，同样相较于对比例，其循环性能和倍率性能更好，表明含BAP的硅碳负极材料的性能提升的效果更明显。
3、本申请实施例通过加酸、还原剂浸出电池黑粉，得到主要含石墨的不溶渣，将得到的石墨粉可以两重使用，降低了制备成本，一方面用于Li f -Si@C-R sO t/B-Z aO b中的碳源，来源直接，另一方面当做嵌锂处理中电解的阴极材料。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1为本申请实施例3硅碳负极材料的SEM图；
图2为本申请对比例2硅碳负极材料的SEM图；
图3为本申请实施例1、3与对比例1、2第1-100次放电比容量图。
具体实施方式
以下将结合实施例对本申请的构思及产生的技术效果进行清楚、完整地描述， 以充分地理解本申请的目的、特征和效果。显然，所描述的实施例只是本申请的一部分实施例，而不是全部实施例，基于本申请的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本申请保护的范围。
实施例1
本实施例的硅碳负极材料，其化学式为Li 0.02 -Si@C-ZrO 2/B-Al 2O 3。
本实施例的硅碳负极材料的制备方法，具体步骤如下：
(1)石墨粉：将NCM型动力电池回收热解、筛分得到150g电池黑粉，加入1.5L的2.63mol/L硫酸调pH＝0.02，再加入20g亚硫酸钠搅拌、过滤得到34g不溶渣，水洗至中性，将4g不溶渣和20ml甘油混合，送至粉碎机中粉碎得到石墨粉，石墨粉粒度<5μm，用粉末压片机压制，得到长片石墨；
(2)制备片状Si@C-ZrO 2/B：将40g硅溶胶(二氧化硅含量27.3％)、0.3g硫酸锆和0.3ml的4-硼酸酯-4',4'-二甲基三苯胺用超声波混合器混合、搅拌，期间加入3g石墨粉，得到均相的Si@C-Zr(SO 4) 2/4-硼酸酯-4',4'-二甲基三苯胺前体，在115℃烘箱烘至恒重、再在210℃充氮气下加热5h、降温、洗涤，得到10g黑色粉末Si@C-ZrO 2/B；
(3)将锂离子导体膜分隔电解槽为两个半槽(阴极半槽、阳极半槽)，阴极半槽中电极为阴极石墨，石墨附着10g的Si@C-ZrO 2/B材料，加400ml导电剂(二甲基乙二醇：碳酸乙烯酯：1.5M六氟磷酸锂按照体积比为1：1.5：1混合)组成，阳极半槽中电极为铝片，阳极半槽中有电解液为400ml0.064mol/L的Li 2SiO 3，通电25min，进行嵌锂处理，阴极半槽固液分离，固体洗涤、在115℃烘箱烘干，得到10.2gLi 0.02 -Si@C-ZrO 2/B；
(4)将阳极半槽的电解液滴加0.37M氢氧化锂得到沉淀，固液分离，固体为Al(OH)3，将0.3gAl(OH) 3与8gLi 0.02 -Si@C-ZrO 2/B混合均匀，再在219℃充氮气下加热3h，得到的硅碳负极材料Li 0.02 -Si@C-ZrO 2/B-Al 2O 3。
本实施例的嵌锂化学反应过程为：
0.03·1/2Li 2SiO 3+Si@C-ZrO 2/B+0.03·1/3Al→Li 0.02-Si@C-ZrO 2/B+0.03·1/3Al 3++0.01·1/2Li 2SiO 3。
实施例2
本实施例的硅碳负极材料，其化学式为Li 0.02-Si@C-NiO/B-Al 2O 3。
本实施例的硅碳负极材料的制备方法，具体步骤如下：
(1)石墨粉：将NCM型动力电池回收热解、筛分得到150g电池黑粉，加入1.5L的2.63mol/L硫酸调pH＝0.02，再加入25g亚硫酸钠搅拌、过滤得到34g不溶渣，水洗至中性，将4g不溶渣和20ml甘油混合，送至粉碎机中粉碎得到石墨粉，石墨粉粒度<5μm，用粉末压片机压制，得到长片石墨；
(2)制备片状Si@C-NiO/B：将45g硅溶胶(二氧化硅含量27.3％)、0.2g硫酸镍和0.3ml的4-硼酸酯-4',4'-二甲基三苯胺用超声波混合器混合、搅拌，期间加入4g石墨粉，得到均相的Si@C-NiSO 4/4-硼酸酯-4',4'-二甲基三苯胺前体，在115℃烘箱烘至恒重、再在210℃充氮气下加热5h、降温、洗涤，得到10g黑色粉末Si@C-NiO/B；
(3)将锂离子导体膜分隔电解槽为两个半槽(阴极半槽、阳极半槽)，阴极半槽中电极为阴极石墨，石墨附着10g的Si@C-NiO/B材料，加400ml导电剂(二甲基乙二醇：碳酸乙烯酯：1.5mol/L六氟磷酸锂按照体积比为1：1.5：1混合)组成，阳极半槽中电极为铝片，阳极半槽中有电解液为400ml0.064mol/L的Li 2SiO 3，通电35min，进行嵌锂处理，阴极半槽固液分离，固体洗涤、在115℃烘箱烘干，得到10.2gLi 0.02 -Si@C-NiO/B；
(4)将阳极半槽的电解液滴加0.37M氢氧化锂得到沉淀，固液分离，固体为Al(OH)3，将0.3gAl(OH) 3与8gLi 0.02 -Si@C-NiO/B混合均匀，再在219℃充氮气下加热3h，得到的硅碳负极材料Li 0.02 -Si@C-NiO/B-Al 2O 3。
实施例3
本实施例的硅碳负极材料，其化学式为Li 0.03-Si@C-MnO/B-MgO。
本实施例的硅碳负极材料的制备方法，具体步骤如下：
(1)石墨粉：将NCM型动力电池回收热解、筛分得到150g电池黑粉，加入1.5L的2.63mol/L硫酸调pH＝0.02，再加入28g亚硫酸钠搅拌、过滤得到34g不溶渣，水洗至中性，将4g不溶渣和20ml甘油混合，送至粉碎机中粉碎得到石墨粉，石墨粉粒度<5μm，用粉末压片机压制，得到长片石墨；
(2)制备片状Si@C-MnO/B：将45g硅溶胶(二氧化硅含量27.3％)、0.4g硫酸锰和0.4ml的4-硼酸酯-4',4'-二甲基三苯胺用超声波混合器混合、搅拌，期间加 入3g石墨粉，得到均相的Si@C-NiSO 4/4-硼酸酯-4',4'-二甲基三苯胺前体，在115℃烘箱烘至恒重、再在260℃充氮气下加热4h、降温、洗涤，得到13g黑色粉末Si@C-NiO/B；
(3)将锂离子导体膜分隔电解槽为两个半槽(阴极半槽、阳极半槽)，阴极半槽中电极为阴极石墨，石墨附着10g的Si@C-NiO/B材料，加480ml导电剂(二甲基乙二醇：碳酸乙烯酯：1.5mol/L六氟磷酸锂按照体积比为1：1.5：1混合)组成，阳极半槽中电极为铝片，阳极半槽中有电解液为480ml0.087mol/L的Li 2SiO 3，通电48min，进行嵌锂处理，阴极半槽固液分离，固体洗涤、在115℃烘箱烘干，得到10.2gLi 0.02 -Si@C-NiO/B；
(4)将阳极半槽的电解液滴加0.18mol/L氢氧化锂得到沉淀，固液分离，固体为Mg(OH) 2，将0.22gMg(OH) 2与9gLi 0.02 -Si@C-NiO/B混合均匀，再在286℃充氮气下加热2h，得到的硅碳负极材料Li 0.03-Si@C-MnO/B-MgO。
实施例4
本实施例的硅碳负极材料，其化学式为Li 0.03-Si@C-MnO/B-MgO。
本实施例的硅碳负极材料的制备方法，具体步骤如下：
(1)石墨粉：将NCM型动力电池回收热解、筛分得到150g电池黑粉，加入1.5L的2.63mol/L硫酸调pH＝0.02，再加入32g亚硫酸钠搅拌、过滤得到34g不溶渣，水洗至中性，将4g不溶渣和20ml甘油混合，送至粉碎机中粉碎得到石墨粉，石墨粉粒度<5μm，用粉末压片机压制，得到长片石墨；
(2)制备片状Si@C-CuO/B：将45g硅溶胶(二氧化硅含量27.3％)、0.15g氯化铜和0.4ml的4-硼酸酯-4',4'-二甲基三苯胺用超声波混合器混合、搅拌，期间加入3g石墨粉，得到均相的Si@C-CuCl 2/B,B'-噻吩[3,2-B]噻吩-2,5-二酰基双[硼酸]前体，在115℃烘箱烘至恒重、再在260℃充氮气下加热4h、降温、洗涤，得到11g黑色粉末Si@C-CuO/B；
(3)将锂离子导体膜分隔电解槽为两个半槽(阴极半槽、阳极半槽)，阴极半槽中电极为阴极石墨，石墨附着10g的Si@C-NiO/B材料，加480ml导电剂(二甲基乙二醇：碳酸乙烯酯：1.5mol/L六氟磷酸锂按照体积比为1：1.5：1混合)组成，阳极半槽中电极为铝片，阳极半槽中有电解液为480ml0.087mol/L的Li 2SiO 3，通电48min，进行嵌锂处理，阴极半槽固液分离，固体洗涤、在115℃ 烘箱烘干，得到10.4gLi 0.04 -Si@C-CuO/B；
(4)将阳极半槽的电解液滴加0.18mol/L氢氧化锂得到沉淀，固液分离，固体为Mg(OH) 2，将0.37gMg(OH) 2与8gLi 0.02 -Si@C-NiO/B混合均匀，再在360℃充氮气下加热2h，得到的硅碳负极材料Li 0.04-Si@C-CuO/B-MgO。
对比例1(未嵌锂处理)
本对比例的硅碳负极材料，其化学式为Li 0.02 -Si@C-ZrO 2/B-Al 2O 3。
本对比例的硅碳负极材料的制备方法，具体步骤如下：
(1)石墨粉：将NCM型动力电池回收热解、筛分得到150g电池黑粉，加入1.5L的2.63mol/L硫酸调pH＝0.02，再加入25g亚硫酸钠搅拌、过滤得到34g不溶渣，水洗至中性，将4g不溶渣和20ml甘油混合，送至粉碎机中粉碎得到石墨粉，石墨粉粒度<5μm，用粉末压片机压制，得到长片石墨；
(2)制备片状Si@C-ZrO 2/B：将40g硅溶胶(二氧化硅含量27.3％)、0.3g硫酸锆和0.3ml的4-硼酸酯-4',4'-二甲基三苯胺用超声波混合器混合、搅拌，期间加入3g石墨粉，得到均相的Si@C-Zr(SO 4) 2/4-硼酸酯-4',4'-二甲基三苯胺前体，在115℃烘箱烘至恒重、再在210℃充氮气下加热5h、降温、洗涤，得到10g黑色粉末Si@C-ZrO 2/B。
对比例2(未加入硼酸聚合物)
本对比例的硅碳负极材料，其化学式为Li 0.03-Si@C-MnO/B-MgO。
本对比例的硅碳负极材料的制备方法，具体步骤如下：
(1)石墨粉：将NCM型动力电池回收热解、筛分得到150g电池黑粉，加入1.5L的2.63mol/L硫酸调pH＝0.02，再加入20g亚硫酸钠搅拌、过滤得到34g不溶渣，水洗至中性，将4g不溶渣和20ml甘油混合，送至粉碎机中粉碎得到石墨粉，石墨粉粒度<5μm，用粉末压片机压制，得到长片石墨；
(2)制备片状Si@C-MnO/B：将45g硅溶胶(二氧化硅含量27.3％)、0.4g硫酸锰和0.4ml的4-硼酸酯-4',4'-二甲基三苯胺用超声波混合器混合、搅拌，期间加入3g石墨粉，得到均相的Si@C-MnSO 4/4-硼酸酯-4',4'-二甲基三苯胺前体，在115℃烘箱烘至恒重、再在260℃充氮气下加热4h、降温、洗涤，得到13g黑色粉末Si@C-MnO/B；
(3)将锂离子导体膜分隔电解槽为两个半槽(阴极半槽、阳极半槽)，阴极半 槽中电极为阴极石墨，石墨附着10g的Si@C-MnO/B材料，加480ml导电剂(二甲基乙二醇：碳酸乙烯酯：1.5mol/L六氟磷酸锂按照体积比为1：1.5：1混合)组成，阳极半槽中电极为铝片，阳极半槽中有电解液为480ml0.087mol/L的Li 2SiO 3，通电48min，进行嵌锂处理，阴极半槽固液分离，固体洗涤、在115℃烘箱烘干，得到10.2gLi 0.02 -Si@C-MnO/B；
(4)将阳极半槽的电解液滴加0.18mol/L氢氧化锂得到沉淀，固液分离，固体为Mg(OH) 2，将0.22gMg(OH) 2与9gLi 0.02 -Si@C-MnO混合均匀，再在286℃充氮气下加热2h，得到的硅碳负极材料Li 0.03-Si@C-MnO-MgO。
实施例1-4与对比例1-2分析：
图1为对比例2硅碳负极材料的SEM图，可见对比例2制备得到的硅碳负极材料Li 0.03-Si@C-MnO-MgO快状、片状较多，快状硅碳负极材料大小为5μm左右，图2实施例3硅碳负极材料的SEM图，可见实施例3制备得到的硅碳负极材料Li 0.03-Si@C-MnO/B-MgO片状较多，快状很少，片状硅碳负极材料大小为400-800nm左右。
表1为实施例1-3与对比例1、2硅碳负极材料比表面积、D50，实施例1-3制备得到的硅碳负极材料的比表面积、D50优于对比例1、2硅碳负极材料的比表面积、D50。此外，对比例1制备得到的硅碳负极材料的比表面积高于对比例2硅碳负极材料的比表面积，对比例1制备得到的硅碳负极材料的D50高于对比例2硅碳负极材料的D50，说明加硼酸聚合物(BAP)后的硅碳负极材料的比表面积、D 50更佳。
实施例1、3与对比例1、2分析：
电极的制备采用了电化学方法，首先是极片制备：把实施例1、实施例3、对比例1、2制备得到的硅碳负极活性物质、Super P导电剂、粘结剂，按照8：1.5：0.5的质量比，用电子天平称取，放置于特定称量瓶中，分散均匀，用超纯水做溶剂，使用磁力搅拌器把浆料混匀，之后把配置好的浆料通过涂布机进行涂覆，集流体采用铜箔，置于燥箱中85℃处理8h。最后再使用切片机切片，获得直径约12mm的可用于电化学测试的极片。
扣式电池组装：计算极片的活性物质载量，把极片转移至手套箱，准备按着电极壳，硅负极，隔膜，金属锂对电极，泡沫镍的顺序依次叠放，然后进行 扣电组装。半电池组装好后，压力封装。封装完后，需要把扣式电池置于室温下静置过夜。测试时保持测试环境为室温(15-25℃)，电压范围为0.001-1.5V，电流密度设为0.5A/g、1A/g、1.5A/g、3A/g，循环次数为100次，见图3。
表1 实施例1-4与对比例1-2硅碳负极比表面积、电导率
组别 BET(m 2/g) D 90(μm) D 50(μm)
实施例1 0.481 1.22 0.69
实施例2 0.468 1.24 0.68
实施例3 0.446 1.01 0.64
实施例4 0.455 1.33 0.67
对比例1 0.363 1.56 0.83
对比例2 0.247 7.43 3.73
图3实施例1、3与对比例1、2第1-100次放电比容量图，结合表1以及图3，0.5A/g电流密度下，实施例1、3第1次放电比容量分别达到2259mAh/g、2647mAh/g，对比例1、2第1次放电比容量分别达到1798mAh/g、2302mAh/g，3A/g电流密度下，循环次数达到31次时，实施例1、3放电比容量达到1473mAh/g、1289mAh/g，对比例1、2第31次时放电比容量为601mAh/g、1018mAh/g，实施例1、3表现出优异的倍率及循环性能。实施例1、3制备得到的硅碳负极比表面积、D 50、D 90均优于于对比例1-2制备得到的硅碳负极比表面积、D 50、D 90，尤其是对比例2制备得到的硅碳负极比表面积、D 50、D 90高于比例1制备得到的硅碳负极比表面积、D 50、D 90，说明经过硼酸聚合物(BAP)处理的硅碳负极的性能更优。
上面结合附图对本申请实施例作了详细说明，但是本申请不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本申请宗旨的前提下作出各种变化。此外，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。

Claims (13)

  1. 一种硅碳负极材料，其中，所述硅碳负极材料的化学通式为Li f -Si@C-R sO t/B-Z aO b；所述R为锆、铜、镍、钴、锰、铬、钛、钼、银、镁、钙、锗、锡、锑中至少一种；所述Z为铝、镁、锌中的至少一种，其中s、t分别独立的为1、2、3、4或5，a＝1或2，b＝1或3。
  2. 根据权利要求1所述的硅碳负极材料，其中，所述Z aO b为Al 2O 3、MgO、ZnO中的一种。
  3. 根据权利要求1所述的硅碳负极材料，其中，所述R sO t为ZrO 2、NiO、MnO、CuO中的至少一种。
  4. 根据权利要求1所述的硅碳负极材料，其中，所述硅碳负极材料为Li 0.04 -Si@C-CuO/B-MgO、Li 0.03 -Si@C-MnO/B-MgO、Li 0.02 -Si@C-ZrO 2/B-Al 2O 3、Li 0.02 -Si@C-NiO/B-Al 2O 3中的至少一种。
  5. 权利要求1-4任一项所述的硅碳负极材料的制备方法，其中，所述的制备方法用于制备权利要求1-4任一项所述的硅碳负极材料。
  6. 根据权利要求5所述的硅碳负极材料的制备方法，其包括以下步骤：
    将硅溶胶、可溶性R盐和硼酸聚合物混合搅拌，再加入石墨粉混合，反应，得到Si@C-R盐/BAP前体，热处理，得到Si@C-R sO t/B；
    在石墨块为阴极、金属Z为阳极的电解槽中，用锂离子导体膜分隔电解槽为两个半槽，分别为阴极半槽和阳极半槽，将Si@C-R sO t/B置于阴极半槽通电电解，进行嵌锂处理，将阴极半槽固液分离，固体洗涤、烘干，得到Li f -Si@C-R sO t/B；
    向阳极半槽中的电解液加入锂源搅拌，反应，固液分离，取固相与所述Li f -Si@C-R sO t/B混合均匀，再进行热处理，得到所述硅碳负极材料。
  7. 根据权利要求6所述的硅碳负极材料的制备方法，其中，所述石墨块是由以下方法制备得到：将动力电池回收热解、筛分，得到电池黑粉，加硫酸调pH，并加入还原剂搅拌，固液分离，取固相水洗，再加入分散剂混合，粉碎，压制成型，得到石墨块。
  8. 根据权利要求7所述的硅碳负极材料的制备方法，其中，所述还原剂为焦硫酸钠、焦硫酸钾、亚硫酸钠、亚硫酸钾、硫代硫酸钠、硫代硫酸钾中的至少一种。
  9. 根据权利要求7所述的硅碳负极材料的制备方法，其中，所述分散剂为蛋 白液、甘油、苯甲酸中的至少一种。
  10. 根据权利要求6所述的硅碳负极材料的制备方法，其中，所述可溶性R盐为锆、铜、镍、钴、锰、铬、钛、钼、银、镁钙、锗、锡、锑的可溶性的硫酸盐、硝酸盐、磷酸盐、氯化盐、溴化盐中的至少一种。
  11. 根据权利要求6所述的硅碳负极材料的制备方法，其中，所述硼酸聚合物为4-硼酸酯-4',4'-二甲基三苯胺、B,B'-噻吩[3,2-B]噻吩-2,5-二酰基双[硼酸]中的至少一种。
  12. 根据权利要求6所述的硅碳负极材料的制备方法，其中，所述锂源为氢氧化锂、氯化锂、硫酸锂、硝酸锂中的至少一种。
  13. 一种电池，其中，包括权利要求1-4任一项所述的硅碳负极材料。
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