WO2023134366A1 - Silicon-carbon negative electrode material, and preparation method therefor and use thereof - Google Patents

Silicon-carbon negative electrode material, and preparation method therefor and use thereof 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)
Chinese (zh)
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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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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to GB2314846.3A priority Critical patent/GB2619868A/en
Publication of WO2023134366A1 publication Critical patent/WO2023134366A1/en

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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
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/48—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
    • 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
    • H01M4/48—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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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.

Abstract

The present application relates to the technical field of lithium ion batteries, and discloses a silicon-carbon negative electrode material, and a preparation method therefor and a use thereof. The chemical general formula of the silicon-carbon negative electrode material is Lif -Si@C-RsOt/B-ZaOb; R is at least one of zirconium, copper, nickel, cobalt, manganese, chromium, titanium, molybdenum, silver, magnesium, calcium, germanium, tin, and antimony; Z is at least one of aluminum, magnesium, and zinc; s and t each are independently 1, 2, 3, 4 or 5; a is equal to 1 or 2, and b is equal to 1 or 3. According to the silicon-carbon negative electrode material of the present application, because a boric acid polymer (BAP) is contained, the specific surface area and D50 of the silicon-carbon negative electrode material are better, and then the electrochemical properties are improved.

Description

硅碳负极材料及其制备方法和应用Silicon carbon negative electrode material and its preparation method and application 技术领域technical field
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。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.
背景技术Background technique
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。In recent years, because the release of some metals and electrolytes in waste power batteries is harmful to the environment, and based on the limited resources of lithium-ion batteries, relevant recycling companies have increased the recycling of waste power batteries. Common recyclable materials in waste power batteries are positive electrode materials such as lithium cobalt oxide, lithium iron phosphate and cobalt nickel manganese oxide, current collector materials such as copper and aluminum foil, and negative electrode materials such as graphite. Among them, graphite is a key anode material. Therefore, it is very important to develop an efficient recycling process for recovering graphite from scrap power batteries, which can reduce the impact of mining on the environment and improve the recycling rate of graphite resources.
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。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. At present, during the lithium-deintercalation process of silicon-based negative electrode materials, 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. In addition, 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.
发明内容Contents of the invention
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。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
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。The embodiment of this application proposes a silicon-carbon negative electrode material and its preparation method and application. The silicon-carbon negative electrode material solves the problems of large volume change of the silicon negative electrode, damage to the material structure, and functional failure of the negative electrode. Recycling graphite waste and improving the value of efficient utilization of negative electrode materials.
本申请实施例中提供以下技术方案：The following technical solutions are provided in the embodiments of this application:
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。 A silicon-carbon negative electrode material whose general chemical formula is Li f - Si@CR s O t /BZ a O b ; the R is zirconium, copper, nickel, cobalt, manganese, chromium, titanium, molybdenum, silver, magnesium , calcium, germanium, tin, antimony at least one; said Z is at least one of aluminum, magnesium, zinc, wherein s, t are independently 1, 2, 3, 4 or 5, a=1 or 2, b=1 or 3.
优选地，所述R为锆、铜、镍、钴、锰、铬、钛、钼、银中至少一种。Preferably, the R is at least one of zirconium, copper, nickel, cobalt, manganese, chromium, titanium, molybdenum and silver.
优选地，所述Z aO b为Al 2O 3、MgO、ZnO中的一种。 Preferably, the Z a O b is one of Al 2 O 3 , MgO and ZnO.
优选地，所述R sO t为ZrO 2、NiO、MnO、CuO中的至少一种。 Preferably, the R s O t is at least one of ZrO 2 , NiO, MnO, and CuO.
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。 Preferably, 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 .
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。A method for preparing a silicon-carbon negative electrode material. The preparation method is used to prepare the above-mentioned silicon-carbon negative electrode material.
一种硅碳负极材料的制备方法，包括以下步骤：A method for preparing a silicon-carbon negative electrode material, comprising the steps of:
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； Mix and stir silica sol, soluble R salt and boric acid polymer, then add graphite powder to mix, react to obtain Si@CR salt/BAP precursor, heat treatment to obtain Si@CR s O 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； In the electrolytic cell where the graphite block is the cathode and the metal Z is the anode, the electrolytic cell is divided into two half-cells with a lithium ion conductor membrane, which are the cathode half-cell and the anode half-cell respectively, and the Si@CR s O t /B is placed The cathode half cell is energized and electrolyzed, and lithium intercalation treatment is performed, the cathode half cell is separated from solid and liquid, the solid is washed and dried, and Li f - Si@CR s O t /B is obtained;
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。 Add a lithium source to the electrolyte in the anode half-cell, stir, react, separate solid and liquid, take the solid phase and mix it with the Li f - Si@CR s O t /B evenly, and then perform heat treatment to obtain the silicon carbon negative electrode material .
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。Preferably, 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.
进一步优选地，所述电池黑粉和硫酸的固液比为100-300g/L。Further preferably, the solid-to-liquid ratio of the battery black powder to sulfuric acid is 100-300 g/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。Further preferably, the concentration of sulfuric acid is 1-10 mol/L; more preferably, the concentration of sulfuric acid is 5-10 mol/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。Preferably, the reducing agent is at least one of sodium pyrosulfate, potassium pyrosulfate, sodium sulfite, potassium sulfite, sodium thiosulfate, and potassium thiosulfate.
进一步优选地，所述还原剂和硫酸的固液比为10-100g/L。Further preferably, the solid-to-liquid ratio of the reducing agent and sulfuric acid is 10-100 g/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。Further preferably, the dispersant is at least one of protein solution, glycerin, and benzoic acid.
进一步优选地，所述固相和分散剂的固液比为30-400g/L。Further preferably, the solid-to-liquid ratio of the solid phase and the dispersant is 30-400 g/L.
进一步优选地，所述石墨粉的粒度<5μm。Further preferably, the particle size of the graphite powder is <5 μm.
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。Preferably, 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.
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。Preferably, the amount of R added in the soluble R salt is 0.01-0.10 of the total mass of silica sol and graphite.
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。Preferably, the soluble R salts are soluble sulfates, nitrates, phosphates, and chlorides of zirconium, copper, nickel, cobalt, manganese, chromium, titanium, molybdenum, silver, magnesium calcium, germanium, tin, and antimony , at least one of bromide salts.
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。Preferably, the boronic acid polymer is 4-boronate-4',4'-dimethyltriphenylamine, B,B'-thiophene[3,2-B]thiophene-2,5-diacylbis[ at least one of boric acid].
优选地，所述热处理的温度为200-400℃，热处理的时间为2-6h。Preferably, the heat treatment temperature is 200-400° C., and the heat treatment time is 2-6 hours.
优选地，所述活性金属Z为镁、铝、锰、锌中的至少一种。Preferably, the active metal Z is at least one of magnesium, aluminum, manganese and zinc.
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。Preferably, the lithium ion conductor membrane is characterized in that only lithium ions can pass through during electrolysis.
优选地，所述阴极半槽中由Si@C-R sO t/B材料、导电剂组成。 Preferably, the cathode half-cell is composed of Si@CR s O t /B material and conductive agent.
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。Further preferably, the conductive agent is mixed with dimethyl glycol, ethylene carbonate, and lithium hexafluorophosphate in a volume ratio of 1:1.5:1.
更优选地，所述六氟磷酸锂的浓度为1.5-2mol/L。More preferably, the concentration of the lithium hexafluorophosphate is 1.5-2 mol/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。 Further preferably, Si@CR s O t /B material is attached near the cathode potential in the cathode half-cell.
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。 Further preferably, the solid-to-liquid ratio of the Si@CR s O t /B material and the conductive agent is 10-50 g/L.
优选地，所述控制阴极、阳极电势为阴极、阳极电势差>2.5V。Preferably, the potential difference between the cathode and anode of the control is >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。Preferably, the anode half-cell electrolyte is a lithium silicate solution, and the concentration of the lithium silicate solution is 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。 Further preferably, 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 .
优选地，所述固相、Li f-Si@C-R sO t/B的质量比为(0.1-5)：100。 Preferably, the mass ratio of the solid phase, Li f -Si@CR s O t /B is (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：The applicant studies using lithium silicate as the electrolyte in the lithium intercalation solution and the lithium source for lithium intercalation treatment to perform lithium intercalation treatment. The lithium intercalation treatment can be expressed as follows:
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。 e·1/jLi j Si k O l +Si@CR s O t /B+f·1/X·Z→Li f - Si@CR s O t /B+f·1/X·Z X+ +( ef) 1/jLi j Si k O l .
优选地，所述热处理的温度为200-400℃，热处理的时间为2-6h。Preferably, the heat treatment temperature is 200-400° C., and the heat treatment time is 2-6 hours.
优选地，所述热处理的气氛为氮气。Preferably, the atmosphere of the heat treatment is nitrogen.
本申请还提供一种电池，包括所述的硅碳负极材料。The present application also provides a battery, including the silicon-carbon negative electrode material.
相对于相关技术，本申请实施例的有益效果如下：Compared with related technologies, the beneficial effects of the embodiments of the present application are as follows:
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。 1. The silicon-carbon anode material provided in the embodiment of the present application contains Si@CR s O t /B, which makes the specific surface area and D50 of the silicon-carbon anode material better, thereby improving the electrochemical performance.
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。 2. In the embodiment of the present application, in the preparation of Si@CR s O t /B, the stability performance is improved by blending silica sol, graphite powder and boric acid high polymer (BAP). The main reason is that the BAP molecule contains Coordination bond in NB, silica sol, graphite powder and BAP were blended and compounded to obtain Si@CR s O t /B. The influence of volume change is small, and there are many contact points, so the ion diffusion method is optimized (SEM images in Figure 1-3, compared with the comparative example), and the cycle performance and rate performance are also better than the comparative example. , indicating that the performance improvement effect of BAP-containing silicon-carbon anode materials is more obvious.
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。 3. In the embodiment of the present application, the battery black powder is leached by adding acid and reducing agent to obtain insoluble slag mainly containing graphite, and the obtained graphite powder can be double-used, which reduces the preparation cost. On the one hand, it is used for Li f - Si@CR The carbon source in s O t /BZ a O b is directly sourced, and on the other hand, it is used as the cathode material for electrolysis in lithium intercalation treatment.
在阅读并理解了附图和详细描述后，可以明白其他方面。Other aspects will be apparent to others upon reading and understanding the drawings and detailed description.
附图说明Description of drawings
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。The accompanying drawings are used to provide a further understanding of the technical solutions herein, and constitute a part of the description, and are used together with the embodiments of the application to explain the technical solutions herein, and do not constitute limitations to the technical solutions herein.
图1为本申请实施例3硅碳负极材料的SEM图；Fig. 1 is the SEM figure of the silicon carbon negative electrode material of embodiment 3 of the present application;
图2为本申请对比例2硅碳负极材料的SEM图；Fig. 2 is the SEM picture of the silicon carbon negative electrode material of comparative example 2 of the present application;
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。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.
具体实施方式Detailed ways
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。The idea and technical effects of the present application will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present application. Apparently, the described embodiments are only some of the embodiments of the present application, not all of them. Based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative efforts belong to The protection scope of this application.
实施例1Example 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。 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 .
本实施例的硅碳负极材料的制备方法，具体步骤如下：The preparation method of the silicon carbon negative electrode material of the present embodiment, the specific steps are as follows:
(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；(1) Graphite powder: recycle, pyrolyze and sieve the NCM type power battery to obtain 150g of battery black powder, add 1.5L of 2.63mol/L sulfuric acid to adjust pH=0.02, then add 20g of sodium sulfite to stir, filter to obtain 34g of insoluble residue, wash with water To neutrality, mix 4g of insoluble slag and 20ml of glycerin, send it to a pulverizer to pulverize to obtain graphite powder, the particle size of graphite powder is <5 μm, and press it with a powder tablet press to obtain long graphite flakes;
(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； (2) Preparation of flake Si@C-ZrO 2 /B: 40g of silica sol (silica content 27.3%), 0.3g of zirconium sulfate and 0.3ml of 4-boronate-4',4'-dimethyl The base triphenylamine was mixed and stirred with an ultrasonic mixer, and 3g of graphite powder was added during the process to obtain a homogeneous Si@C-Zr(SO 4 ) 2 /4-boronate-4',4'-dimethyltriphenylamine Body, baked in an oven at 115°C to constant weight, then heated at 210°C for 5h under nitrogen, cooled, and washed to obtain 10g of black powder 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； (3) Separate the electrolytic cell into two half-cells (cathode half-cell and anode half-cell) by the lithium-ion conductor membrane. 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, and the electrolyte in the anode half tank is 400ml0. 064 mol/L Li 2 SiO 3 , electrified for 25 minutes, lithium intercalation treatment, solid-liquid separation in the cathode half-cell, solid washing, and oven drying at 115°C to obtain 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。 (4) Add 0.37M lithium hydroxide dropwise to the electrolyte in the anode half-cell to obtain precipitation, solid-liquid separation, the solid is Al(OH)3, mix 0.3gAl(OH) 3 with 8gLi 0.02 - Si@C-ZrO 2 / B was mixed evenly, and then heated at 219°C for 3 hours under nitrogen gas to obtain the silicon-carbon anode material Li 0.02 - Si@C-ZrO 2 /B-Al 2 O 3 .
本实施例的嵌锂化学反应过程为：The lithium intercalation chemical reaction process of the present embodiment is:
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。 0.03·1/2Li 2 SiO 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 2 SiO 3 .
实施例2Example 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。 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 .
本实施例的硅碳负极材料的制备方法，具体步骤如下：The preparation method of the silicon carbon negative electrode material of the present embodiment, the specific steps are as follows:
(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；(1) Graphite powder: Recycle and pyrolyze the NCM type power battery and sieve to obtain 150g of battery black powder, add 1.5L of 2.63mol/L sulfuric acid to adjust pH=0.02, then add 25g of sodium sulfite to stir, filter to obtain 34g of insoluble residue, wash with water To neutrality, mix 4g of insoluble slag and 20ml of glycerin, send it to a pulverizer to pulverize to obtain graphite powder, the particle size of graphite powder is <5 μm, and press it with a powder tablet press to obtain long graphite flakes;
(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； (2) Preparation of flake Si@C-NiO/B: 45g of silica sol (silica content 27.3%), 0.2g of nickel sulfate and 0.3ml of 4-boronate-4',4'-dimethyl Triphenylamine was mixed and stirred with an ultrasonic mixer, during which 4g of graphite powder was added to obtain a homogeneous precursor of Si@C-NiSO 4 /4-boronic acid ester-4',4'-dimethyltriphenylamine at 115°C Dry in an oven to constant weight, then heat at 210°C for 5h under nitrogen gas, cool down, and wash to obtain 10g of black powder 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； (3) Separate the electrolytic cell into two half-cells (cathode half-cell and anode half-cell) by the lithium-ion conductor membrane. 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. .064mol/L Li 2 SiO 3 , energized for 35 minutes, lithium intercalation treatment, solid-liquid separation in the cathode half-cell, solid washing, and oven drying at 115°C to obtain 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。 (4) Add 0.37M lithium hydroxide dropwise to the electrolyte in the anode half-cell to obtain precipitation, solid-liquid separation, the solid is Al(OH)3, mix 0.3gAl(OH) 3 with 8gLi 0.02 - Si@C-NiO/B Mix evenly, and then heat at 219°C for 3 hours under nitrogen gas to obtain the silicon-carbon anode material Li 0.02 - Si@C-NiO/B-Al 2 O 3 .
实施例3Example 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。 The silicon carbon negative electrode material of this embodiment has a chemical formula of 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：The preparation method of the silicon carbon negative electrode material of the present embodiment, the specific steps are as follows:
(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；(1) Graphite powder: recycle, pyrolyze and sieve the NCM type power battery to obtain 150g of battery black powder, add 1.5L of 2.63mol/L sulfuric acid to adjust pH=0.02, then add 28g of sodium sulfite to stir, filter to obtain 34g of insoluble residue, wash with water To neutrality, mix 4g of insoluble slag and 20ml of glycerin, send it to a pulverizer to pulverize to obtain graphite powder, the particle size of graphite powder is <5 μm, and press it with a powder tablet press to obtain long graphite flakes;
(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； (2) Preparation of flake Si@C-MnO/B: 45g of silica sol (silica content 27.3%), 0.4g of manganese sulfate and 0.4ml of 4-boronate-4',4'-dimethyl Triphenylamine was mixed and stirred with an ultrasonic mixer, during which 3g of graphite powder was added to obtain a homogeneous precursor of Si@C-NiSO 4 /4-boronic acid ester-4',4'-dimethyltriphenylamine at 115°C Dry in an oven to constant weight, then heat at 260°C for 4 hours under nitrogen gas, cool down, and wash to obtain 13g of black powder 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； (3) Separate the electrolytic cell into two half-cells (cathode half-cell and anode half-cell) by the lithium-ion conductor membrane. 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. .087mol/L Li 2 SiO 3 , energized for 48 minutes, lithium intercalation treatment, solid-liquid separation in the cathode half-cell, solid washing, and oven drying at 115°C to obtain 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。 (4) Add 0.18mol/L lithium hydroxide dropwise to the electrolyte in the anode half-cell to obtain a precipitate, separate the solid from the liquid, and the solid is Mg(OH) 2 , mix 0.22gMg(OH) 2 with 9gLi 0.02 - Si@C-NiO /B mixed evenly, and then heated at 286°C for 2h under nitrogen gas to obtain the silicon-carbon anode material Li 0.03 -Si@C-MnO/B-MgO.
实施例4Example 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。 The silicon carbon negative electrode material of this embodiment has a chemical formula of 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：The preparation method of the silicon carbon negative electrode material of the present embodiment, the specific steps are as follows:
(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；(1) Graphite powder: recycle, pyrolyze and sieve the NCM type power battery to obtain 150g of battery black powder, add 1.5L of 2.63mol/L sulfuric acid to adjust pH=0.02, then add 32g of sodium sulfite to stir, filter to obtain 34g of insoluble residue, wash with water To neutrality, mix 4g of insoluble slag and 20ml of glycerin, send it to a pulverizer to pulverize to obtain graphite powder, the particle size of graphite powder is <5 μm, and press it with a powder tablet press to obtain long graphite flakes;
(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； (2) Preparation of flake Si@C-CuO/B: 45g of silica sol (silica content 27.3%), 0.15g of copper chloride and 0.4ml of 4-boronate-4',4'-dimethyl Triphenylamine was mixed and stirred with an ultrasonic mixer, and 3g of graphite powder was added during the process to obtain a homogeneous Si@C-CuCl 2 /B,B'-thiophene[3,2-B]thiophene-2,5-diacylbis [Boronic acid] precursor was dried in an oven at 115°C to constant weight, then heated at 260°C for 4h under nitrogen, cooled, and washed to obtain 11g of black powder 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； (3) Separate the electrolytic cell into two half-cells (cathode half-cell and anode half-cell) by the lithium-ion conductor membrane. 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. .087mol/L of Li 2 SiO 3 , energized for 48 minutes, lithium intercalation treatment, solid-liquid separation in the cathode half-cell, solid washing, and oven drying at 115°C to obtain 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。 (4) Add 0.18mol/L lithium hydroxide dropwise to the electrolyte in the anode half-cell to obtain a precipitate, separate the solid from the liquid, and the solid is Mg(OH) 2 , mix 0.37gMg(OH) 2 with 8gLi 0.02 - Si@C-NiO /B mixed evenly, and then heated at 360°C for 2h under nitrogen gas to obtain the silicon-carbon anode material Li 0.04 -Si@C-CuO/B-MgO.
对比例1(未嵌锂处理)Comparative example 1 (without lithium intercalation treatment)
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。 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 .
本对比例的硅碳负极材料的制备方法，具体步骤如下：The preparation method of the silicon carbon negative electrode material of this comparative example, concrete steps are as follows:
(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；(1) Graphite powder: Recycle and pyrolyze the NCM type power battery and sieve to obtain 150g of battery black powder, add 1.5L of 2.63mol/L sulfuric acid to adjust pH=0.02, then add 25g of sodium sulfite to stir, filter to obtain 34g of insoluble residue, wash with water To neutrality, mix 4g of insoluble slag and 20ml of glycerin, send it to a pulverizer to pulverize to obtain graphite powder, the particle size of graphite powder is <5 μm, and press it with a powder tablet press to obtain long graphite flakes;
(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。 (2) Preparation of flake Si@C-ZrO 2 /B: 40g of silica sol (silica content 27.3%), 0.3g of zirconium sulfate and 0.3ml of 4-boronate-4',4'-dimethyl The base triphenylamine was mixed and stirred with an ultrasonic mixer, and 3g of graphite powder was added during the process to obtain a homogeneous Si@C-Zr(SO 4 ) 2 /4-boronate-4',4'-dimethyltriphenylamine body, dried in an oven at 115°C to constant weight, then heated at 210°C for 5h under nitrogen, cooled, and washed to obtain 10g of black powder Si@C-ZrO 2 /B.
对比例2(未加入硼酸聚合物)Comparative example 2 (do not add boric acid polymer)
本对比例的硅碳负极材料，其化学式为Li 0.03-Si@C-MnO/B-MgO。 The silicon-carbon anode material of this comparative example has a chemical formula of 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：The preparation method of the silicon carbon negative electrode material of this comparative example, concrete steps are as follows:
(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；(1) Graphite powder: recycle, pyrolyze and sieve the NCM type power battery to obtain 150g of battery black powder, add 1.5L of 2.63mol/L sulfuric acid to adjust pH=0.02, then add 20g of sodium sulfite to stir, filter to obtain 34g of insoluble residue, wash with water To neutrality, mix 4g of insoluble slag and 20ml of glycerin, send it to a pulverizer to pulverize to obtain graphite powder, the particle size of graphite powder is <5 μm, and press it with a powder tablet press to obtain long graphite flakes;
(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； (2) Preparation of flake Si@C-MnO/B: 45g of silica sol (silica content 27.3%), 0.4g of manganese sulfate and 0.4ml of 4-boronate-4',4'-dimethyl Triphenylamine was mixed and stirred with an ultrasonic mixer, during which 3g of graphite powder was added to obtain a homogeneous precursor of Si@C-MnSO 4 /4-boronic acid ester-4',4'-dimethyltriphenylamine at 115°C Dry in an oven to constant weight, then heat at 260°C for 4h under nitrogen, cool down, and wash to obtain 13g of black powder 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； (3) Separate the electrolytic cell into two half-cells (cathode half-cell, anode half-cell) by the lithium ion conductor membrane, 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. .087mol/L Li 2 SiO 3 , energized for 48 minutes, lithium intercalation treatment, solid-liquid separation in the cathode half-cell, solid washing, and oven drying at 115°C to obtain 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。 (4) Add 0.18mol/L lithium hydroxide dropwise to the electrolyte in the anode half-cell to obtain a precipitate, separate the solid from the liquid, and the solid is Mg(OH) 2 , mix 0.22gMg(OH) 2 with 9gLi 0.02 - Si@C-MnO Mix evenly, and then heat at 286°C for 2h under nitrogen gas to obtain the silicon-carbon anode material Li 0.03 -Si@C-MnO-MgO.
实施例1-4与对比例1-2分析：Embodiment 1-4 and comparative example 1-2 analyze:
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。 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 μm, 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.
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。 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. In addition, the specific surface area 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, and 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.
实施例1、3与对比例1、2分析：Embodiment 1,3 and comparative example 1,2 analyze:
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。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.
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。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.
表1 实施例1-4与对比例1-2硅碳负极比表面积、电导率Table 1 Example 1-4 and comparative example 1-2 silicon carbon negative electrode specific surface area, electrical conductivity
组别group BET(m 2/g) BET(m 2 /g) D 90(μm) D90 (μm) D 50(μm) D50 (μm)
实施例1Example 1 0.4810.481 1.221.22 0.690.69
实施例2Example 2 0.4680.468 1.241.24 0.680.68
实施例3Example 3 0.4460.446 1.011.01 0.640.64
实施例4Example 4 0.4550.455 1.331.33 0.670.67
对比例1Comparative example 1 0.3630.363 1.561.56 0.830.83
对比例2Comparative example 2 0.2470.247 7.437.43 3.733.73
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。 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.
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。The embodiments of the present application have been described in detail above in conjunction with the accompanying drawings, but the present application is not limited to the above-mentioned embodiments, and within the scope of knowledge of those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present application. Variety. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other under the condition of no conflict.

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。 A silicon-carbon negative electrode material, wherein the general chemical formula of the silicon-carbon negative electrode material is Li f - Si@CR s O t /BZ a O b ; the R is zirconium, copper, nickel, cobalt, manganese, chromium , titanium, molybdenum, silver, magnesium, calcium, germanium, tin, antimony at least one; said Z is at least one of aluminum, magnesium, zinc, wherein s, t are independently 1, 2, 3, 4 or 5, a=1 or 2, b=1 or 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。 The silicon-carbon negative electrode material according to claim 1, wherein the Z a O b is one of Al 2 O 3 , MgO, and ZnO.
  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。 The silicon carbon negative electrode material according to claim 1, wherein the R s O t is at least one of ZrO 2 , NiO, MnO, and CuO.
  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。 The silicon-carbon negative electrode material according to claim 1, wherein 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 - At least one of Si@C-ZrO 2 /B-Al 2 O 3 , Li 0.02 - Si@C-NiO/B-Al 2 O 3 .
  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。The preparation method of the silicon-carbon negative electrode material according to any one of claims 1-4, wherein the preparation method is used to prepare the silicon-carbon negative electrode material according to any one of claims 1-4.
  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：The preparation method of silicon carbon negative electrode material according to claim 5, it comprises the following steps:
    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； Mix and stir silica sol, soluble R salt and boric acid polymer, then add graphite powder to mix, react to obtain Si@CR salt/BAP precursor, heat treatment to obtain Si@CR s O 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； In the electrolytic cell where the graphite block is the cathode and the metal Z is the anode, the electrolytic cell is divided into two half-cells with a lithium ion conductor membrane, which are the cathode half-cell and the anode half-cell respectively, and the Si@CR s O t /B is placed The cathode half cell is energized and electrolyzed, and lithium intercalation treatment is performed, the cathode half cell is separated from solid and liquid, the solid is washed and dried, and Li f - Si@CR s O t /B is obtained;
    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。 Add a lithium source to the electrolyte in the anode half-cell, stir, react, separate solid and liquid, take the solid phase and mix it with the Li f - Si@CR s O t /B evenly, and then perform heat treatment to obtain the silicon carbon negative electrode material .
  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。The preparation method of silicon-carbon negative electrode material according to claim 6, wherein, the graphite block is prepared by the following method: recovering the power battery, pyrolyzing and sieving to obtain battery black powder, adding sulfuric acid to adjust the pH, and adding Stir the reducing agent, separate the solid from the liquid, take the solid phase and wash it with water, then add a dispersant to mix, pulverize, press and shape to obtain a graphite block.
  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。The preparation method of silicon carbon negative electrode material according to claim 7, wherein, the reducing agent is at least one of sodium pyrosulfate, potassium pyrosulfate, sodium sulfite, potassium sulfite, sodium thiosulfate, potassium thiosulfate .
  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。The preparation method of silicon carbon negative electrode material according to claim 7, wherein, said dispersant is at least one in protein solution, glycerin, benzoic acid.
  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。The preparation method of silicon-carbon negative electrode material according to claim 6, wherein, the soluble R salt is zirconium, copper, nickel, cobalt, manganese, chromium, titanium, molybdenum, silver, magnesium calcium, germanium, tin, antimony At least one of soluble sulfates, nitrates, phosphates, chlorides, and bromides.
  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。The preparation method of silicon-carbon negative electrode material according to claim 6, wherein, the boric acid polymer is 4-boric acid ester-4',4'-dimethyltriphenylamine, B,B'-thiophene[3, At least one of 2-B]thiophene-2,5-diacylbis[boronic acids].
  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。The method for preparing a silicon-carbon negative electrode material according to claim 6, wherein the lithium source is at least one of lithium hydroxide, lithium chloride, lithium sulfate, and lithium nitrate.
  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。A battery, comprising the silicon-carbon negative electrode material according to any one of claims 1-4.
PCT/CN2022/138579 2022-01-14 2022-12-13 Silicon-carbon negative electrode material, and preparation method therefor and use thereof WO2023134366A1 (en)

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