CN113363432A - Negative plate containing silicon-based negative electrode material with high initial coulombic efficiency and lithium ion battery - Google Patents

Negative plate containing silicon-based negative electrode material with high initial coulombic efficiency and lithium ion battery Download PDF

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CN113363432A
CN113363432A CN202110429981.1A CN202110429981A CN113363432A CN 113363432 A CN113363432 A CN 113363432A CN 202110429981 A CN202110429981 A CN 202110429981A CN 113363432 A CN113363432 A CN 113363432A
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negative electrode
sio
silicon
coulombic efficiency
high initial
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石先兴
张小祝
许梦清
陈军
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Wanxiang A123 Systems Asia Co Ltd
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Wanxiang Group Corp
Wanxiang A123 Systems Asia Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of lithium batteries, and discloses a silicon-based negative electrode material with high initial coulombic efficiency, which comprises the following steps: 1. carbon coating; 2. with LiAlH4Mixing materials; 3. pyrolyzing, washing and drying to obtain composite SiOyA material of/C, wherein 0<y<1, namely the silicon-based negative electrode material with high initial coulombic efficiency. The invention also discloses a negative plate containing the silicon-based negative electrode material with high initial coulombic efficiency, which comprises a copper foil, wherein the surface of the copper foil is coated with negative electrode slurry, the negative electrode slurry comprises a negative electrode active substance, a conductive agent and a binder, and the negative electrode comprises a negative electrode active substance, a conductive agent and a binderThe active substance is composite SiOythe/C material or the material mixed with graphite. The invention uses LiAlH as a strong reducing agent4Controllable regulation of SiOxThe ratio of Si to O in the material improves SiOxThe material has the advantages of high first charge-discharge efficiency, low raw material cost, easy realization of industrialization, less introduced 'electrochemical inertia' impurities and small influence on the conductivity of the silicon-based material.

Description

Negative plate containing silicon-based negative electrode material with high initial coulombic efficiency and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a negative plate containing a silicon-based negative electrode material with high initial coulombic efficiency and a lithium ion battery.
Background
In the lithium ion battery cathode material, the silicon-based material has the advantages of second only to the theoretical capacity of metallic lithium, lower lithium intercalation potential, lower price and the like, so that the silicon-based material is an ideal choice for replacing graphite. However, pure silicon materials have serious volume effect problems after lithium intercalation, and the cycle life is far shorter than that of graphite materials, thereby preventing the commercial application of the pure silicon materials. Silicon oxide (SiO)x，0<x<2, approaching to 1) not only has high specific capacity, but also has much smaller volume effect than pure silicon, has better stability and cycle life, and has already appeared small-scale commercial application in the fields of digital, power batteries and the like. SiO 2xThe cycle stability is improved compared with that of simple substance Si, but SiOxThe material can form lithium oxide during the first lithium intercalation process to generate Li2O and Li4SiO4More lithium ions are consumed, a large amount of lithium elements lose activity and become dead lithium, the initial coulomb efficiency of the battery is low, and the improvement of the specific energy of the power battery is influenced. To solve the problem of SiOxThe problem of low coulombic efficiency of the negative electrode for the first time, and a lithium supplement technology becomes a necessary way. From the technical path, the currently mainstream lithium supplement schemes can be divided into three main categories: 1) the negative electrode is supplemented with lithium, mainly inert metal lithium powder and metal lithium foil; 2) the positive electrode being lithium-supplemented, primarily by some lithium-containing oxides, e.g. Li5FeO4Etc.; 3) lithium is supplemented by lithium-containing compounds, wherein the lithium compounds are divided into two categories, and the first category, such as Stabilized Lithium Metal Powder (SLMP), is applied to prelithiation, mainly by two ways: in thatAdding the slurry in the slurry mixing process or directly adding the slurry to the surface of the negative plate; the second category is nano lithium silicide powder, which has a small size and is more conducive to dispersion in the negative electrode. In addition, the electrode is already in an expanded state, and the volume change in the circulation process does not influence the structure of the whole electrode. The use of metallic lithium is involved whether lithium foil, SLMP or lithium silicide powder is used to supplement lithium. However, the metallic lithium has high reactivity and is very sensitive to water, so that a large safety risk exists, and the application is very difficult in practice. In addition, lithium metal is expensive, highly reactive, difficult to handle, and requires high costs for storage and transportation for protection. If the lithium supplementing process does not involve metal lithium, the cost can be saved, and the safety performance can be improved.
Currently for SiOxThe problem that the first charge-discharge efficiency of the material is low (-77%) in the application of the lithium ion battery is to improve SiOxThe first charge-discharge efficiency is obtained by mixing Li or Mg with SiOxHeating after mixing to prepare simple substance Si (90 percent) and Li with higher first charge-discharge efficiency4SiO4Or Mg2SiO4. However, the conventional process has the disadvantage that electrochemically inert silicon-based compounds, such as Li, are formed in the resulting product4SiO4Or Mg2SiO4Not only does the gram capacity of Si decrease, but the presence of these by-products, which are more difficult to remove, will decrease the conductivity of the negative electrode.
Chinese patent with application number CN201711455947.1, published 2019, 07, 05 and discloses a high-coulombic-efficiency silicon-carbon negative electrode material, and a preparation method and application thereof, and the preparation method is characterized by comprising the following steps: mixing raw materials, carrying out redox reaction, crushing treatment and vapor deposition to obtain a finished product. Compared with the prior art, the reduction degree of the silicon monoxide can be controlled by regulating and controlling the addition amount of the reducing agent; the conductivity of the material obtained by the invention is close to that of graphite, the silicon nanoparticles and the uniform buffer structure with controllable content are arranged in the particles, the first coulombic efficiency is more than 87%, the specific capacity is more than 1400mAh/g, the defect of low first efficiency of the silicon oxide material is overcome, and the material has a good application prospect.
But using alloy powder to reduce SiOxThe resulting product will form electrochemically inert Si-based compounds, such as Li4SiO4Or Mg2SiO4Not only does the gram capacity of Si decrease, but the presence of these by-products, which are more difficult to remove, will decrease the conductivity of the negative electrode.
Disclosure of Invention
In order to solve the technical problems, the invention provides a negative plate containing a silicon-based negative electrode material with high initial coulombic efficiency and a lithium ion battery. Adding a certain proportion of strong reducing agent LiAlH4To control SiOxThe ratio of Si to O in the material reduces the oxygen content without damaging SiOxSystem structure, SiO enhancementxCoulombic efficiency of the material during first charge and discharge. The method has high safety coefficient and lower cost than the lithium supplementing technology directly using the metallic lithium.
The specific technical scheme of the invention is as follows: a silicon-based negative electrode material with high initial coulombic efficiency is prepared by the following steps:
step one, carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction, and cooling to room temperature after the reaction is finished to obtain SiOxA material of/C, wherein 0<x<2；
Step two, mixing materials: coating with carbon to obtain SiOxAdding reducing agent into the material/C, and fully and uniformly mixing, wherein the reducing agent is LiAlH4；
Step three, pyrolysis: calcining and reducing the uniformly mixed material in the second step in the protective gas atmosphere, and naturally cooling to obtain the SiO after controllable reductionyA material of/C, wherein 0<y<1；
Step four, washing with water: soaking the pyrolysis product in the third step in dilute hydrochloric acid, cleaning, filtering, washing and drying to obtain the final product composite SiOythe/C material is the silicon-based negative electrode material with high initial coulombic efficiency.
The carbon layer is coated on the surface of the silicon-based material, so that the surface defects of the silicon-based material are effectively reduced, the particle size is improved, and the core-shell structure is formed to reduce the specific surface area of the silicon-based material and improve the quality of the silicon-based materialThe compatibility with electrolyte improves the conductivity and uniformity of the material, thereby improving the cycle performance of the silicon-based material. When the reducing agent reacts with SiOxAfter the/C material is uniformly mixed, the reducing agent is uniformly infiltrated into SiOxIn the/C material, the reduction reaction is carried out with SiO to generate Si simple substance and by-product, thus improving SiOxThe proportion of Si and O in the material and the increase of Si content are beneficial to improving the lithium insertion capacity of the material, the generated by-product can inhibit the volume expansion of the pure silicon material after lithium insertion, the stress caused by volume change is reduced, the material pulverization is reduced, the cycle life is prolonged, and the by-product can be washed away by dilute hydrochloric acid and deionized water, so that the existence of the by-product which is difficult to remove is avoided, the introduction of 'electrochemical inert' impurities into the cathode material is reduced, and the influence on the conductivity of the cathode material is small.
Using LiAlH4The reaction equation as the reducing agent is: LiAlH4+2SiO＝LiAlO2+2Si+2H2℃,. wherein LiAlO2Can be washed away by dilute hydrochloric acid and deionized water, avoids the existence of byproducts which are difficult to remove, reduces the introduction of impurities with electrochemical inertia into the cathode material, has small influence on the conductivity of the cathode material, has low cost of raw materials, and is easy to realize industrialized application.
Preferably, the SiO in step onexThe mass percentage of carbon coating in the/C material is 2-8 wt%.
The carbon coating content is too low, so that the surface defects of the silicon-based material cannot be effectively reduced, and the specific surface area of the silicon-based material is not obviously improved; the carbon coating content is too high, the processing performance of the negative electrode material is influenced, the tap density is reduced, the negative electrode material is not easy to be pressed to a specified thickness during rolling, and the negative electrode material is easy to fall off from a copper foil, so that the material falling condition is caused.
Preferably, the SiO in step onexThe mass ratio of the/C material to the reducing agent is 200: 20-100.
SiO can be controlled by controlling the addition amount of the reducing agentxThe ratio of SiO in the/C material reduced to Si is controlled, thereby controlling the SiOxDegree of reduction of the/C material.
Preferably, the carbon source in the first step is one of asphalt, methane, ethylene and acetylene.
Preferably, the protective gas in the first step is argon or nitrogen, and the reaction time is 2-5 hours.
Preferably, the gas flow rate in the third step is 100-120mL/min, the heating rate is 5-8 ℃/min, the reaction temperature is 500-550 ℃, and the heat preservation time is 1-1.5 hours.
The common method is to mix Li or Mg with SiOxHeating after mixing to prepare simple substances Si and Li with high first charge-discharge efficiency4SiO4Or Mg2SiO4However, the temperature is usually 500 ℃ and 1300 ℃, and the invention uses the LiAlH which is a strong reducing agent4To adjust SiOxThe ratio of Si to O in the material can be used for preparing SiO at lower temperatureyA material of/C, wherein 0<y<1。
The negative plate comprises a copper foil, wherein the surface of the copper foil is coated with negative slurry, the negative slurry comprises a negative active substance, a conductive agent and a binder, and the negative active substance is composite SiOya/C material, or composite SiOyA material of mixed material of/C material and graphite.
Preferably, the mass ratio of the negative electrode active material, the conductive agent and the binder is 10-92: 1-70: 7-20.
Preferably, the binder is sodium carboxymethylcellulose and styrene butadiene rubber, and the mass ratio of the sodium carboxymethylcellulose to the styrene butadiene rubber is 1: 2-2.5 or sodium hydroxymethyl cellulose, styrene-butadiene rubber and polyacrylate, wherein the mass ratio of the sodium hydroxymethyl cellulose to the styrene-butadiene rubber to the polyacrylate is 1: 1.5: 0.5-1.
The invention also provides a lithium ion battery containing the silicon-based negative electrode material with high initial coulombic efficiency, which comprises the negative electrode plate.
Compared with the prior art, the method has the beneficial effect that the strong reducing agent LiAlH is adopted4To adjust SiOxThe ratio of Si to O in the material can obviously improve SiOxThe first charge-discharge efficiency of the material is low, and the method is easy to realize and has low raw material costIs applied in industrialization, introduces less electrochemically inert impurities and has no toxic or side effect on SiOxThe conductivity of the active material has less influence.
Drawings
FIG. 1 shows the results of the cycle performance tests of CR2032 type coin cells obtained in examples 1 and 2.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the present invention is further described in detail with reference to the following detailed description. The devices, connections, and methods referred to in this disclosure are those known in the art, unless otherwise indicated.
Example 1
1) Carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction in a tubular furnace, cooling to room temperature after the reaction is finished, and obtaining SiO with the carbon coating mass percentage of 5 wt%xC material, SiO after coatingxThe reversible gram capacity of the/C material is 1620mAh/g, wherein 0<x<2；
2) Mixing materials: 200g of carbon-coated SiO are takenxmaterial/C, 40g of reducing agent LiAlH is added4Fully and uniformly mixing in ball milling tank equipment;
3) pyrolysis: putting the uniformly mixed materials into a tube furnace, introducing nitrogen, raising the temperature to 500 ℃ at the speed of 5 ℃/min at the gas flow rate of 120mL/min, preserving the temperature for 1 hour, continuously introducing the nitrogen, and naturally cooling after the calcination and reduction are finished to obtain SiOyA material of/C, wherein 0<y<1；
4) Washing with water: soaking the pyrolysis product in 80g of dilute hydrochloric acid for 30 minutes, washing for 3 times by 400g of deionized water, adding 60g of ethanol, filtering and washing, and drying at 100 ℃ to obtain the final product, namely the composite SiOythe/C material is a composite silicon-based negative electrode material.
5) And (3) negative electrode slurry: pouring carboxymethylcellulose sodium (CMC) powder into the aqueous solution, and quickly stirring (3000rpm) uniformly (the mass percent of CMC is 3%); adding 14% of conductive agent Super P (SP) into the solution, and rapidly stirring for 2 hours; adding 80% of composite silicon-based negative electrode material into the conductive liquid, slowly stirring for 10min, rapidly stirring for 1 hour, adding a proper amount of deionized water to adjust the stirring consistency (1500mPa & s), and rapidly stirring for 1 hour; adding a certain amount of Styrene Butadiene Rubber (SBR), quickly stirring for 2 hours, slowly stirring for 30min, and removing bubbles (the mass percent of the SBR is 3%); sieving the slurry by a 120-mesh sieve, and controlling the solid content of the slurry to be 45 +/-5%; viscosity 3000 +/-500 mPa.s;
6) negative pole piece: coating the negative electrode slurry on a copper foil, and arranging 5 temperature detection points around: coating speed of 2.5 m/min at 80 deg.C, 90 deg.C, and 80 deg.C, with blowing, and water content controlled below 100ppm in coating workshop; controlling the relative vacuum degree value of the vacuum oven to be less than or equal to-0.1 MPa, and treating for 60min at 115 ℃; rolling the silicon-carbon active material coated on the copper foil by a rolling machine, and controlling the compaction density to be 1.4-2.0g/cm3。
Punching the silicon-based negative electrode plate containing the polymer coating into a pole piece with the diameter of 12mm, taking a metal lithium plate as a counter electrode and a reference electrode in a glove box, wherein the thickness of a PE (polyethylene) diaphragm is 25 mu M, and the electrolyte is LiPF (lithium ion plasma) with the concentration of 1.15M6the/EC + DMC (1: 1), additive 10% FEC, assembled CR2032 model coin cell in argon atmosphere.
Example 2
1) Carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction in a tubular furnace, cooling to room temperature after the reaction is finished, and obtaining SiO with the carbon coating mass percentage of 5 wt%xC material, SiO after coatingxThe reversible gram capacity of the/C material is 1620mAh/g, wherein 0<x<2；
2) Mixing materials: 200g of carbon-coated SiO are takenxmaterial/C, 40g of reducing agent LiAlH is added4Fully and uniformly mixing in ball milling tank equipment;
3) pyrolysis: putting the uniformly mixed materials into a tube furnace, introducing nitrogen, raising the temperature to 500 ℃ at the speed of 5 ℃/min at the gas flow rate of 120mL/min, preserving the temperature for 1 hour, continuously introducing the nitrogen, and naturally cooling after the calcination and reduction are finished to obtain SiOyA material of/C, wherein 0<y<1；
4) Washing with water: will heat upSoaking the decomposition product in 80g of dilute hydrochloric acid for 30 minutes, cleaning with 400g of deionized water for 3 times, adding 60g of ethanol, filtering, washing, and drying at 100 ℃ to obtain the final product, namely the composite SiOythe/C material is a composite silicon-based negative electrode material.
5) And (3) negative electrode slurry: pouring carboxymethylcellulose sodium (CMC) powder into the aqueous solution, uniformly stirring at a high speed (3000rpm), adding Polyacrylate (PAA), and blending until the solid content of the glue solution is 15%, slowly stirring at a speed (800rpm) for 30min, and defoaming (the mass percent of CMC is 2%, and the mass percent of PAA is 1%); adding 14% of conductive agent Super P (SP) into the glue solution, and rapidly stirring for 2 hours; adding 80% of composite silicon-based negative electrode material into the conductive liquid, slowly stirring for 10min, rapidly stirring for 1 hour, adding a proper amount of deionized water to adjust the stirring consistency (1500mPa & s), and rapidly stirring for 1 hour; adding a certain amount of Styrene Butadiene Rubber (SBR), quickly stirring for 2 hours, slowly stirring for 30min, and removing bubbles (the mass percent of the SBR is 3%); sieving the slurry by a 120-mesh sieve, and controlling the solid content of the slurry to be 45 +/-5%; viscosity 3000 +/-500 mPa.s;
6) negative pole piece: coating the negative electrode slurry on a copper foil, and arranging 5 temperature detection points around: coating speed of 2.5 m/min at 80 deg.C, 90 deg.C, and 80 deg.C, with blowing, and water content controlled below 100ppm in coating workshop; controlling the relative vacuum degree value of the vacuum oven to be less than or equal to-0.1 MPa, and treating for 60min at 115 ℃; rolling the silicon-carbon active material coated on the copper foil by a rolling machine, and controlling the compaction density to be 1.4-2.0g/cm3。
Punching the silicon-based negative electrode plate containing the polymer coating into a pole piece with the diameter of 12mm, taking a metal lithium plate as a counter electrode and a reference electrode in a glove box, wherein the thickness of a PE (polyethylene) diaphragm is 25 mu M, and the electrolyte is LiPF (lithium ion plasma) with the concentration of 1.15M6the/EC + DMC (1: 1), additive 10% FEC, assembled CR2032 model coin cell in argon atmosphere.
Example 3
1) Carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction in a tubular furnace, cooling to room temperature after the reaction is finished, and obtaining SiO with the carbon coating mass percentage of 5 wt%xmaterial/C, after coatingSiOxThe reversible gram capacity of the/C material is 1620mAh/g, wherein 0<x<2；
2) Mixing materials: 200g of carbon-coated SiO are takenxmaterial/C, 40g of reducing agent LiAlH is added4Fully and uniformly mixing in ball milling tank equipment;
3) pyrolysis: putting the uniformly mixed materials into a tube furnace, introducing nitrogen, raising the temperature to 500 ℃ at the speed of 5 ℃/min at the gas flow rate of 120mL/min, preserving the temperature for 1 hour, continuously introducing the nitrogen, and naturally cooling after the calcination and reduction are finished to obtain SiOyA material of/C, wherein 0<y<1；
4) Washing with water: soaking the pyrolysis product in 80g of dilute hydrochloric acid for 30 minutes, washing for 3 times by 400g of deionized water, adding 60g of ethanol, filtering and washing, and drying at 100 ℃ to obtain the final product, namely the composite SiOythe/C material is a composite silicon-based negative electrode material.
5) And (3) negative electrode slurry: pouring carboxymethylcellulose sodium (CMC) powder into the aqueous solution, and quickly stirring (3000rpm) uniformly (the mass percent of CMC is 3%); adding 14% of conductive agent Super P (SP) into the solution, and rapidly stirring for 2 hours; adding 80% of negative electrode active material (8% of composite silicon-based negative electrode material in the negative electrode active material, 92% of graphite and 450mAh/g in gram volume) into the conductive liquid, slowly stirring for 10min, rapidly stirring for 1 hour, adding a proper amount of deionized water to adjust the stirring consistency (1500mPa & s), and rapidly stirring for 1 hour; adding a certain amount of Styrene Butadiene Rubber (SBR), quickly stirring for 2 hours, slowly stirring for 30min, and removing bubbles (the mass percent of the SBR is 3%); sieving the slurry by a 120-mesh sieve, and controlling the solid content of the slurry to be 45 +/-5%; viscosity 3000 +/-500 mPa.s;
6) negative pole piece: coating the negative electrode slurry on a copper foil, and arranging 5 temperature detection points around: coating speed of 2.5 m/min at 80 deg.C, 90 deg.C, and 80 deg.C, with blowing, and water content controlled below 100ppm in coating workshop; controlling the relative vacuum degree value of the vacuum oven to be less than or equal to-0.1 MPa, and treating for 60min at 115 ℃; rolling the silicon-carbon active material coated on the copper foil by a rolling machine, and controlling the compaction density to be 1.4-2.0g/cm3。
Punching the silicon-based negative pole piece containing the polymer coatingCutting into 12mm diameter pole pieces, placing in glove box, using metal lithium pieces as counter electrode and reference electrode, PE diaphragm thickness is 25 μ M, electrolyte is 1.15M LiPF6the/EC + DMC (1: 1), additive 10% FEC, assembled CR2032 model coin cell in argon atmosphere.
Example 4
1) Carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction in a tubular furnace, cooling to room temperature after the reaction is finished, and obtaining SiO with the carbon coating mass percentage of 5 wt%xC material, SiO after coatingxThe reversible gram capacity of the/C material is 1620mAh/g, wherein 0<x<2；
2) Mixing materials: 200g of carbon-coated SiO are takenxmaterial/C, 40g of reducing agent LiAlH is added4Fully and uniformly mixing in ball milling tank equipment;
3) pyrolysis: putting the uniformly mixed materials into a tube furnace, introducing nitrogen, raising the temperature to 500 ℃ at the speed of 5 ℃/min at the gas flow rate of 120mL/min, preserving the temperature for 1 hour, continuously introducing the nitrogen, and naturally cooling after the calcination and reduction are finished to obtain SiOyA material of/C, wherein 0<y<1；
4) Washing with water: soaking the pyrolysis product in 80g of dilute hydrochloric acid for 30 minutes, washing for 3 times by 400g of deionized water, adding 60g of ethanol, filtering and washing, and drying at 100 ℃ to obtain the final product, namely the composite SiOythe/C material is a composite silicon-based negative electrode material.
5) And (3) negative electrode slurry: pouring sodium carboxymethylcellulose (CMC) powder into the aqueous solution, adding Polyacrylate (PAA) by fast stirring (3000rpm), and blending until the solid content of the glue solution is 15%, slowly stirring (800rpm) for 30min, and defoaming (the mass percent of CMC is 2%, and the mass percent of PAA is 1%); adding 14% of conductive agent Super P (SP) into the glue solution, and rapidly stirring for 2 hours; adding 80% of negative electrode active material (8% of composite silicon-based negative electrode material in the negative electrode active material, 92% of graphite and 450mAh/g in gram volume) into the conductive liquid, slowly stirring for 10min, rapidly stirring for 1 hour, adding a proper amount of deionized water to adjust the stirring consistency (1500mPa & s), and rapidly stirring for 1 hour; adding a certain amount of Styrene Butadiene Rubber (SBR), quickly stirring for 2 hours, slowly stirring for 30min, and removing bubbles (the mass percent of the SBR is 3%); sieving the slurry by a 120-mesh sieve, and controlling the solid content of the slurry to be 45 +/-5%; viscosity 3000 +/-500 mPa.s;
6) negative pole piece: coating the negative electrode slurry on a copper foil, and arranging 5 temperature detection points around: coating speed of 2.5 m/min at 80 deg.C, 90 deg.C, and 80 deg.C, with blowing, and water content controlled below 100ppm in coating workshop; controlling the relative vacuum degree value of the vacuum oven to be less than or equal to-0.1 MPa, and treating for 60min at 115 ℃; rolling the silicon-carbon active material coated on the copper foil by a rolling machine, and controlling the compaction density to be 1.4-2.0g/cm3。
Punching the silicon-based negative electrode plate containing the polymer coating into a pole piece with the diameter of 12mm, taking a metal lithium plate as a counter electrode and a reference electrode in a glove box, wherein the thickness of a PE (polyethylene) diaphragm is 25 mu M, and the electrolyte is LiPF (lithium ion plasma) with the concentration of 1.15M6the/EC + DMC (1: 1), additive 10% FEC, assembled CR2032 model coin cell in argon atmosphere.
Example 5
1) Carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction in a tubular furnace, cooling to room temperature after the reaction is finished, and obtaining SiO with the carbon coating mass percentage of 5 wt%xC material, SiO after coatingxThe reversible gram capacity of the/C material is 1620mAh/g, wherein 0<x<2；
2) Mixing materials: 200g of carbon-coated SiO are takenxmaterial/C, 20g of reducing agent LiAlH4Fully and uniformly mixing in ball milling tank equipment;
3) pyrolysis: putting the uniformly mixed materials into a tube furnace, introducing nitrogen, raising the temperature to 500 ℃ at the speed of 5 ℃/min at the gas flow rate of 120mL/min, preserving the temperature for 1 hour, continuously introducing the nitrogen, and naturally cooling after the calcination and reduction are finished to obtain SiOyA material of/C, wherein 0<y<1；
4) Washing with water: soaking the pyrolysis product in 80g of dilute hydrochloric acid for 30 minutes, washing for 3 times by 400g of deionized water, adding 60g of ethanol, filtering and washing, and drying at 100 ℃ to obtain the final product, namely the composite SiOythe/C material is a composite silicon-based negative electrode material.
5) And (3) negative electrode slurry: pouring carboxymethylcellulose sodium (CMC) powder into the aqueous solution, uniformly stirring at a high speed (3000rpm), adding Polyacrylate (PAA), and blending until the solid content of the glue solution is 15%, slowly stirring at a speed (800rpm) for 30min, and defoaming (the mass percent of CMC is 2%, and the mass percent of PAA is 1%); adding 14% of conductive agent Super P (SP) into the glue solution, and rapidly stirring for 2 hours; adding 80% of composite silicon-based negative electrode material into the conductive liquid, slowly stirring for 10min, rapidly stirring for 1 hour, adding a proper amount of deionized water to adjust the stirring consistency (1500mPa & s), and rapidly stirring for 1 hour; adding a certain amount of Styrene Butadiene Rubber (SBR), quickly stirring for 2 hours, slowly stirring for 30min, and removing bubbles (the mass percent of the SBR is 3%); sieving the slurry by a 120-mesh sieve, and controlling the solid content of the slurry to be 45 +/-5%; viscosity 3000 +/-500 mPa.s;
6) negative pole piece: coating the negative electrode slurry on a copper foil, and arranging 5 temperature detection points around: coating speed of 2.5 m/min at 80 deg.C, 90 deg.C, and 80 deg.C, with blowing, and water content controlled below 100ppm in coating workshop; controlling the relative vacuum degree value of the vacuum oven to be less than or equal to-0.1 MPa, and treating for 60min at 115 ℃; rolling the silicon-carbon active material coated on the copper foil by a rolling machine, and controlling the compaction density to be 1.4-2.0g/cm3。
Example 6
1) Carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction in a tubular furnace, cooling to room temperature after the reaction is finished, and obtaining SiO with the carbon coating mass percentage of 5 wt%xC material, SiO after coatingxThe reversible gram capacity of the/C material is 1620mAh/g, wherein 0<x<2；
2) Mixing materials: 200g of carbon-coated SiO are takenxmaterial/C, 100g of reducing agent LiAlH4Fully and uniformly mixing in ball milling tank equipment;
3) pyrolysis: putting the uniformly mixed materials into a tube furnace, introducing nitrogen, raising the temperature to 500 ℃ at the speed of 5 ℃/min at the gas flow rate of 120mL/min, preserving the temperature for 1 hour, continuously introducing the nitrogen, and naturally cooling after the calcination and reduction are finished to obtain SiOyA material of/C, wherein 0<y<1；
4) Washing with water: soaking the pyrolysis product in 80g of dilute hydrochloric acid for 30 minutes, washing for 3 times by 400g of deionized water, adding 60g of ethanol, filtering and washing, and drying at 100 ℃ to obtain the final product, namely the composite SiOythe/C material is a composite silicon-based negative electrode material.
5) And (3) negative electrode slurry: pouring carboxymethylcellulose sodium (CMC) powder into the aqueous solution, uniformly stirring at a high speed (3000rpm), adding Polyacrylate (PAA), and blending until the solid content of the glue solution is 15%, slowly stirring at a speed (800rpm) for 30min, and defoaming (the mass percent of CMC is 2%, and the mass percent of PAA is 1%); adding 14% of conductive agent Super P (SP) into the glue solution, and rapidly stirring for 2 hours; adding 80% of composite silicon-based negative electrode material into the conductive liquid, slowly stirring for 10min, rapidly stirring for 1 hour, adding a proper amount of deionized water to adjust the stirring consistency (1500mPa & s), and rapidly stirring for 1 hour; adding a certain amount of Styrene Butadiene Rubber (SBR), quickly stirring for 2 hours, slowly stirring for 30min, and removing bubbles (the mass percent of the SBR is 3%); sieving the slurry by a 120-mesh sieve, and controlling the solid content of the slurry to be 45 +/-5%; viscosity 3000 +/-500 mPa.s;
6) negative pole piece: coating the negative electrode slurry on a copper foil, and arranging 5 temperature detection points around: coating speed of 2.5 m/min at 80 deg.C, 90 deg.C, and 80 deg.C, with blowing, and water content controlled below 100ppm in coating workshop; controlling the relative vacuum degree value of the vacuum oven to be less than or equal to-0.1 MPa, and treating for 60min at 115 ℃; rolling the silicon-carbon active material coated on the copper foil by a rolling machine, and controlling the compaction density to be 1.4-2.0g/cm3。
Comparative example 1
Comparative example 1 differs from example 1 in that: SiO usedxThe material was directly added to the negative electrode slurry as a negative electrode active material without carbon coating, mixing, pyrolysis, and washing, and the remaining raw materials and processes were the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 2 in that: SiO usedxThe material is directly used as a negative active substance to be added into the negative slurry without carbon coating, material mixing, pyrolysis and washing reaction processes, and other raw materials, processes and materialsExample 2 is the same.
Comparative example 3
Comparative example 3 differs from example 3 in that: SiO usedxThe material is directly mixed with graphite as a negative active material (SiO in the negative active material) without carbon coating, mixing, pyrolysis and washing reaction processesx8% of graphite and 92% of graphite) was added to the negative electrode slurry, and the remaining raw materials and processes were the same as in example 3.
Comparative example 4
Comparative example 4 differs from example 4 in that: SiO usedxThe material is directly mixed with graphite as a negative active material (SiO in the negative active material) without carbon coating, mixing, pyrolysis and washing reaction processesx8% by weight and 92% by weight of graphite) was added to the negative electrode slurry, and the remaining raw materials and processes were the same as in example 4.
TABLE 1
Figure RE-GDA0003109764850000091
The first charge and discharge results of the CR2032 type coin cells prepared in the above examples 1 and 2 and comparative examples 1 and 2 are shown in Table 1, with a test voltage range of 0.005-1.5V and a charge and discharge rate of 0.1C/0.1C.
The test results are shown in table 1: examples 1 and 2 are the use of LiAlH4Batteries made of treated silicon-based negative electrode materials (high first efficiency sample 1), comparative examples 1 and 2 were made using LiAlH-free negative electrode material4The first charge-discharge efficiency (first coulombic efficiency) of the batteries (conventional sample 1) made of the treated silicon-based anode material of examples 1 and 2 was about 6% higher than that of comparative examples 1 and 2, because a certain amount of the strong reducing agent LiAlH was added4Then, SiOxThe SiO in the material can be controllably reduced into Si to obtain SiOythe/C material improves the proportion of Si and O, increases the Si content, is beneficial to improving the lithium insertion capacity of the material, and generates a byproduct LiAlO2The volume expansion of the pure silicon material after lithium embedding can be inhibited, the stress caused by volume change is reduced, the material pulverization is reduced, and the cycle life is prolonged. Example 1 and comparativeExample 1 in the preparation of the battery, only CMC and SBR were added to the negative electrode slurry, in example 2 and comparative example 2, PAA was added to the negative electrode slurry in addition to CMC and SBR, and CMC: SBR: the content ratio of PAA is 1: 1.5: 0.5, this is because of SiOxThe material is added into the cathode slurry after reduction reaction, the binding force of the slurry and the copper foil is changed, and can be obtained by comparing whether PAA is additionally added or not, and comparing example 1 with example 2 (for using LiAlH-modified cathode slurry)4For the battery made of the treated silicon-based negative electrode material (high-performance sample 1): after addition of PAA, the first coulombic efficiency of the cell was essentially unchanged, comparative example 1 and comparative example 2 were compared (for using no LiAlH)4Battery made of treated silicon-based negative electrode material (conventional sample 1)): after adding PAA, the first coulombic efficiency of the cell is basically unchanged.
TABLE 2
Figure RE-GDA0003109764850000101
The first charge and discharge results of the CR2032 type coin cells prepared in the above examples 3 and 4 and comparative examples 3 and 4 are shown in Table 2, with a test voltage range of 0.005-1.5V and a charge and discharge rate of 0.1C/0.1C.
The test results are shown in table 2: in the actual production process of the battery, in order to match the use of the positive electrode material, the silicon-based negative electrode material with overhigh capacity generally needs to be mixed with graphite to be used as the negative electrode material, and examples 3 and 4 use LiAlH4Batteries (high first efficiency sample 2) were prepared by mixing the treated silicon-based negative electrode material with graphite, and comparative examples 3 and 4 were prepared using LiAlH-free lithium ion secondary batteries4The first charge-discharge efficiency (first coulombic efficiency) of examples 3 and 4 was about 2% higher than that of comparative examples 3 and 4 in the battery (conventional sample 2) prepared by mixing the treated silicon-based negative electrode material with graphite, because a certain amount of the strong reducing agent LiAlH was added4Then, SiO in the SiOx material is controllably reduced into Si to obtain the SiOy/C material, the ratio of Si to O is improved, the content of Si is increased, the lithium intercalation capacity of the material is improved, and the generated byproduct LiAlO2Can inhibit the volume of pure silicon material after lithium intercalationExpansion, reduced stress caused by volume change, reduced material pulverization, and prolonged cycle life. Whereas in examples 3 and comparative examples 3, only CMC and SBR were added to the negative electrode slurry during the preparation of the battery, in examples 4 and comparative examples 4, PAA was added to the negative electrode slurry in addition to CMC and SBR, and CMC: SBR: the content ratio of PAA is 1: 1.5: 0.5, this is because of SiOxThe material is added into the cathode slurry after reduction reaction, the binding force of the slurry and the copper foil is changed, and whether PAA is additionally added or not can be obtained by comparison, namely comparison between example 3 and example 4 (for using LiAlH4For the battery made of the treated silicon-based negative electrode material (high-performance sample 2): after adding PAA, the first charge capacity and discharge capacity of the battery are almost unchanged, the first coulombic efficiency is basically unchanged, and a comparison example 3 and a comparison example 4 (for using the non-LiAlH battery)4Battery made of treated silicon-based negative electrode material (conventional sample 2)): after the PAA is added, the first charge capacity and the discharge capacity of the battery are almost unchanged, and the first coulombic efficiency is basically unchanged.
Fig. 1 shows the results of the cycle performance tests of CR2032 type coin cells obtained in examples 1 and 2, under the following conditions: the charge and discharge multiplying power is 1C/0.5C, the voltage range is 2.8-4.2V, and the cycle is 175 times at 45 ℃.
The test result shows that: in example 1, only CMC and SBR were added to the negative electrode slurry, and in example 2, PAA was added to the negative electrode slurry in addition to CMC and SBR, and the ratio of CMC: SBR: the content ratio of PAA is 1: 1.5: 0.5, this is because of SiOxThe material is added into the cathode slurry after reduction reaction, the binding force of the slurry and the copper foil is changed, and can be obtained by comparing whether PAA is additionally added or not, and comparing example 1 with example 2 (for using LiAlH4For the battery made of the treated silicon-based negative electrode material (high-performance sample 1): after PAA was added, the capacity retention of the battery after 175 cycles at 45 ℃ was 93.7%, while the capacity retention of the battery of example 2 without PAA after 175 cycles at 45 ℃ was 90.3%, since PAA effectively adapted to the volume expansion of the silicon material after lithium intercalation, reduced stress due to volume change, reduced material dusting, and CMC and SBRThe mixture of (a) is soft in texture and cannot effectively suppress volume expansion during charging of the battery.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (10)

1. A silicon-based negative electrode material with high initial coulombic efficiency is characterized in that the preparation process comprises the following steps:
step one, carbon coating: mixing SiOxUniformly mixing with a carbon source, introducing protective gas, carrying out vapor deposition reaction, and cooling to room temperature after the reaction is finished to obtain SiOxA material of/C, wherein 0<x<2；
Step two, mixing materials: coating with carbon to obtain SiOxAdding reducing agent into the material/C, and fully and uniformly mixing, wherein the reducing agent is LiAlH4；
Step three, pyrolysis: calcining and reducing the uniformly mixed material in the second step in the protective gas atmosphere, and naturally cooling to obtain the SiO after controllable reductionyA material of/C, wherein 0<y<1；
Step four, washing with water: soaking the pyrolysis product in the third step in dilute hydrochloric acid, cleaning, filtering, washing and drying to obtain the final product composite SiOythe/C material is the silicon-based negative electrode material with high initial coulombic efficiency.
2. The silicon-based negative electrode material with high initial coulombic efficiency as claimed in claim 1, wherein the SiO in the first stepxThe mass percentage of carbon coating in the/C material is 2-8 wt%.
3. The silicon-based negative electrode material with high initial coulombic efficiency as claimed in claim 1, wherein the SiO in the first stepxThe mass ratio of the/C material to the reducing agent is 200: 20-100.
4. The silicon-based anode material with high initial coulombic efficiency as claimed in claim 1, wherein the carbon source in the first step is one of asphalt, methane, ethylene and acetylene.
5. The silicon-based anode material with high initial coulombic efficiency as claimed in claim 1, wherein the protective gas in the first step is argon or nitrogen, and the reaction time is 2-5 hours.
6. The silicon-based anode material with high initial coulombic efficiency as claimed in claim 1, wherein the gas flow rate in step three is 100-120mL/min, the temperature rise rate is 5-8 ℃/min, the reaction temperature is 450-500 ℃, and the heat preservation time is 1-1.5 hours.
7. A negative plate containing the silicon-based negative electrode material with high initial coulombic efficiency of any one of claims 1-6, comprising a copper foil, wherein the surface of the copper foil is coated with negative electrode slurry, the negative electrode slurry comprises a negative electrode active material, a conductive agent and a binder, and the negative electrode active material is composite SiOya/C material, or composite SiOyA material of mixed material of/C material and graphite.
8. The negative electrode sheet according to claim 7, wherein the mass ratio of the negative electrode active material, the conductive agent, and the binder is 10 to 92: 1-70: 7-20.
9. The negative plate as claimed in claim 7, wherein the binder is sodium carboxymethylcellulose and styrene-butadiene rubber, and the mass ratio of the sodium carboxymethylcellulose to the styrene-butadiene rubber is 1: 2-2.5 or sodium hydroxymethyl cellulose, styrene-butadiene rubber and polyacrylate, wherein the mass ratio of the sodium hydroxymethyl cellulose to the styrene-butadiene rubber to the polyacrylate is 1: 1.5: 0.5-1.
10. A lithium ion battery comprising a silicon-based negative electrode material with high initial coulombic efficiency, comprising the negative electrode sheet according to any one of claims 7 to 9.
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