WO2019052572A1 - 一种微胶囊型硅碳复合负极材料及其制备方法和应用 - Google Patents

一种微胶囊型硅碳复合负极材料及其制备方法和应用 Download PDF

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WO2019052572A1
WO2019052572A1 PCT/CN2018/106160 CN2018106160W WO2019052572A1 WO 2019052572 A1 WO2019052572 A1 WO 2019052572A1 CN 2018106160 W CN2018106160 W CN 2018106160W WO 2019052572 A1 WO2019052572 A1 WO 2019052572A1
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silicon
carbon
binder
powder
microcapsule
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PCT/CN2018/106160
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English (en)
French (fr)
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郑洪河
杨思鸣
郑雪莹
张晓辉
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江苏道赢科技有限公司
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Priority to CA3035900A priority Critical patent/CA3035900C/en
Priority to US16/344,480 priority patent/US11335895B2/en
Priority to KR1020197018336A priority patent/KR102239750B1/ko
Priority to JP2019528666A priority patent/JP7030119B2/ja
Publication of WO2019052572A1 publication Critical patent/WO2019052572A1/zh

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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
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/134—Electrodes based on metals, Si 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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
    • H01M4/621—Binders
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of lithium ion battery electrodes, and particularly relates to a microcapsule type silicon carbon composite anode material, a preparation method thereof and application thereof.
  • the silicon material has a high lithium storage capacity, its theoretical capacity is about 4200 mAh / g, and the actual specific capacity is more than 3000 mAh / g, which is very likely to replace graphite materials as an important negative electrode material for the next generation of high-energy lithium batteries.
  • silicon materials undergo a drastic change in the volume of silicon ions during the insertion and extraction of lithium ions, and the expansion ratio can reach 300%, thereby causing the silicon particles to be powdered.
  • the problem of rapid decline in the capacity of the pole piece is that the first Coulomb efficiency of the silicon material is not high, and the third is that the stability of the SEI film on the silicon surface is poor, especially in the process of volume change, which causes damage and growth, resulting in serious lithium consumption.
  • the modification and modification of silicon materials including the particle size control of silicon materials, surface control and compounding with carbon materials
  • the second is to select suitable bonding.
  • Agent system especially the selection of binder system with three-dimensional network type cross-linking structure, including cross-linked alginate system, cross-linked polyacrylamide system, etc., the current research in this area has also achieved good results.
  • the third is the choice of an excellent electrolyte system, especially the electrolyte system containing fluoroethylene carbonate (FEC) shows good performance.
  • FEC fluoroethylene carbonate
  • silicon-carbon composite In the prior art, one of the choices for industrial application of silicon materials is silicon-carbon composite.
  • silicon-carbon composite there are many ways of silicon-carbon composite, including in-situ growth of carbon materials on the surface of silicon materials, including amorphous carbon, carbon nanotubes and Graphene, etc., but the preparation process of this material is very complicated, silicon oxide and silicon carbide are easily formed during the growth of carbon materials, affecting the performance of silicon materials, and the other is the mechanical mixing of silicon particles and carbon materials. It is easy to mix the two evenly, especially the mechanical mixing of silicon powder and graphite material has been industrialized. Generally, about 10% of silicon particles can be mixed in the graphite powder for the production of more than 400mAh/g capacity.
  • Carbon negative electrode sheet although this manufacturing method is simple and easy to implement, the prominent problem is that the capacity of the electrode is rapidly attenuated. After about 200 cycles, the silicon material can hardly perform its proper performance, and the high specific energy battery The longevity of life has a great impact.
  • the Chinese invention patent CN103022448A discloses a method for preparing a silicon battery silicon carbon negative electrode material, comprising the following steps: 1) 50 to 90 parts by weight of micron-sized silicon. The powder is added to the ball mill tank, and the solvent is added to perform ball milling. 2) 10 to 50 parts by weight of natural graphite is added to the step 1) ball-milled industrial silicon powder to continue the ball milling; 3) the step 2) the ball-milled material is dried.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide an improved silicon-carbon composite anode material.
  • the microcapsule-type silicon-carbon composite anode material of the invention has extremely excellent cycle performance, coulombic efficiency and rate performance. Excellent results.
  • the present invention also provides a method of preparing a microcapsule-type silicon-carbon composite anode material.
  • the invention also provides an application of a microcapsule type silicon carbon composite anode material in preparing a lithium ion battery electrode sheet.
  • a microcapsule-type silicon-carbon composite anode material comprising a current collector, and a silicon carbon coating formed by drying a silicon carbon slurry coated on the current collector, the silicon carbon slurry comprising a carbonaceous slurry and a silicon capsule powder dispersed in the carbonaceous slurry, the carbonaceous slurry comprising a dispersant and a carbon material dispersed in the dispersant, a first conductive agent, and a first bond
  • the silicon capsule powder comprises silicon powder and a second binder coated on the surface of the silicon powder, and the second binder and the silicon powder coated thereon form a microcapsule structure; The first binder is different from the second binder.
  • the microcapsule structure is a solid particle or particle formed by coating a surface of the silicon powder with a second binder, wherein the solid particles or particles are made of silicon powder, and the second binder is coated with silicon powder. surface.
  • the first binder and the second binder are insoluble, poorly soluble or slightly Dissolved.
  • the first binder is sodium carboxymethylcellulose and/or styrene butadiene rubber
  • the second binder is selected from the group consisting of alginate, polyacrylate, and Arabian. A combination of one or more of gum, guar gum, and hyaluronate.
  • the second binder is a binder to which calcium ions and/or copper ions are added, wherein the mass fraction of calcium ions and/or copper ions to the second binder is 2 to 15%.
  • the addition of copper ions and/or calcium ions can make the stability and mechanical properties of the outer shell formed by the binder better.
  • other components capable of crosslinking the binder can also be added to obtain The modified binder enables the shell formed by the binder to have strong mechanical properties and stability.
  • the second binder is a binder to which calcium ions and/or copper ions are added, wherein the calcium ion and/or copper ions account for 5 to 12% by mass of the second binder. .
  • the weight ratio of the carbon material to the silicon powder is 2 to 10..1.
  • the silicon powder and the second binder respectively occupy 70 to 95% and 2 to 15% by mass of the raw material of the silicon capsule powder.
  • the carbon material, the first binder, and the first conductive agent respectively occupy 90 to 98%, 1 to 5% of the mass fraction of the carbonaceous slurry, and 0.5 to 5%.
  • the silicon powder is nano-silicon and/or micro-silicon.
  • the carbon material is a combination of one or more selected from the group consisting of natural graphite, artificial graphite, pyrolytic carbon, or hard carbon materials.
  • the dispersing agent is water, or a mixed solvent of an alcohol and water.
  • the first conductive agent is a combination of one or more selected from the group consisting of acetylene black, Super P, Super S, carbon fibers, carbon nanotubes, and graphene.
  • the silicon capsule powder further comprises a second conductive agent selected from the group consisting of acetylene black, Super P, Super S, carbon fiber, carbon nanotubes, and A combination of one or more of graphene.
  • Another technical solution provided by the present invention is a method for preparing a microcapsule-type silicon-carbon composite anode material according to the above, wherein the preparation method comprises the following steps:
  • (a) preparation of a silicon capsule powder dispersing the silicon powder of the silicon capsule powder and the second binder in a dispersant to obtain a siliceous slurry, and then baking the siliceous slurry Drying, grinding, that is, the silicon capsule powder having a microcapsule structure in which the silicon powder is a core and the second binder is an outer shell; wherein a second conductive agent is added to the dispersing agent, or is not added;
  • preparation of a silicon carbon slurry the silicon capsule powder prepared in the step (a) is added to the preparation prepared in the step (b) when the preparation of the carbonaceous slurry is completed, at the completion or after completion.
  • the carbonaceous slurry is mixed and stirred to obtain the silicon carbon slurry;
  • step (d) preparation of a microcapsule-type silicon-carbon composite anode material: the silicon carbon slurry prepared in the step (c) is coated on the current collector, and dried to obtain the microcapsule-type silicon-carbon composite anode material.
  • a microcapsule-type silicon-carbon composite anode material described above is used for preparing a lithium ion battery electrode sheet.
  • the present invention has the following advantages compared with the prior art:
  • the silicon powder and the carbon material are respectively placed in different binder environments, and the silicon powder is completely coated by the second binder to form a microcapsule structure, so that the activities of silicon and carbon are maximized.
  • the long-term cycle performance of the electrode sheet is greatly improved, and the original 200-time significant attenuation is increased to almost no attenuation, the internal resistance of the electrode sheet is significantly reduced, the rate performance is greatly improved, and the mechanical stability of the electrode sheet is remarkably improved.
  • the first coulombic efficiency of the electrode sheet is greatly improved, and therefore the silicon carbon negative electrode material of the present invention is of great significance for the development of future high specific energy and long life lithium ion batteries.
  • the present invention proposes a silicon-carbon composite anode material having a microcapsule structure, and in particular, firstly, a binder suitable for silicon particles is mixed and dispersed together with silicon particles in silicon.
  • the surface of the particle is uniformly coated with a binder having good compatibility, and the stability of the binder is preferably further strengthened by a crosslinking technique to form a binder which is modified by crosslinking with silicon particles as a core.
  • the microcapsule structure of the outer shell is further based on the preparation of the basic carbon fiber (graphite) slurry, and the silicon capsule powder is added and stirred to uniformly disperse the silicon capsule powder in the carbonaceous slurry, thus forming a Silicon in a suitable binder for silicon, carbon in a binder suitable for carbon (preferably between the two different binders is insoluble, poorly soluble or slightly soluble, but without a distinct phase interface)
  • the silicon carbon slurry is formed, and then the silicon carbon slurry is coated on the current collector, and dried to obtain a microcapsule type silicon-carbon composite anode material, which can be processed into an electrode sheet for a lithium ion battery, and the electrode sheet protrudes.
  • the preparation method of the silicon-carbon composite negative electrode material of the microcapsule structure of the invention comprises the following steps: (a) using silicon powder (using a common nano or micro silicon powder for a lithium battery), a second binder, and a second conductive agent. (preferably, or not) dispersed in a dispersant, stirred and mixed to obtain a siliceous slurry, and then the siliceous slurry is dried at a suitable temperature (preferably 60 to 90 ° C), and then ground.
  • the silicon powder is a core
  • the second binder is a microcapsule structure of the silicon capsule powder
  • the second binder is selected from the group consisting of alginate, polyacrylate, gum arabic, melon a mixture of one or more of guar gum and hyaluronic acid salt
  • the first binder is selected from the group consisting of sodium carboxymethylcellulose and/or styrene-butadiene rubber
  • the silicon capsule is added when the preparation of the carbonaceous slurry is about to be completed, when it is completed, or after completion.
  • the powder is further stirred for about 30 minutes to obtain a silicon carbon slurry; (d) the obtained silicon carbon slurry is applied to the current collecting In a body, the coating thickness is preferably 40 to 200 ⁇ m, and drying (preferably 60 ° C), that is, a microcapsule-type silicon-carbon composite negative electrode material is obtained.
  • a second binder rich in carboxyl or hydroxyl groups which is advantageous for film formation on the silicon surface to improve the first coulombic efficiency of the material.
  • the second binder is added with calcium ions.
  • a binder of copper ions wherein the calcium ion and/or copper ion accounts for 2 to 15% by mass of the second binder, more preferably, wherein calcium ions and/or copper ions account for
  • the mass fraction of the second binder is 5 to 12%, and the copper ions and/or calcium ions are added in the form of CaCl 2 , CaSO 4 , CuCl 2 , CuSO 4 , etc., and further crosslinking of the binder not only reduces the The possibility of dissolving in the carbonaceous slurry can also inhibit the volume effect of silicon during the cycle. When it is mixed with the carbonaceous slurry, the silicon and carbon can be in the best binder environment. It is beneficial to improve the electrical properties of the electrode sheets.
  • the first and second conductive agents are each a mixture of one or more selected from the group consisting of acetylene black, Super P, Super S, carbon fibers, and carbon nanotubes; and the dispersing agents used in the steps (a) and (b) can be used. It is a mixed solvent of water, or water and an alcohol solvent. Wherein, the weight ratio between the carbon material and the silicon powder is controlled to be 2 to 10..1, and the silicon powder and the second binder respectively account for 70 to 95%, 2 to 15 of the mass of the silicon capsule powder.
  • the silicon capsule powder further comprises a second conductive agent in a mass fraction of 0.01 to 15% of the silicon capsule powder; the carbon material, the second binder, and the second conductive agent
  • the mass fraction of the carbonaceous slurry is 90 to 98%, 1 to 5%, and 0.5 to 5%, respectively.
  • This embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method:
  • the obtained microcapsule-type silicon-carbon composite anode material is made into a negative electrode sheet, and a lithium sheet is used as a counter electrode to assemble a 2032 button type battery.
  • the electrolyte is 1M LiPF 6 is a conductive salt having a volume ratio of 1:1:1. /DMC/DEC solution, and add FEC which accounts for 10% of the electrolyte as an additive; seal the assembled battery, and after standing, test the electrochemical performance of the constant current on the charge and discharge tester (where the charge and discharge rates are both It is 0.2C and the voltage range is 0.01 ⁇ 1V).
  • the present embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in the embodiment 1, except that in the step (a), the silicon powder and the seaweed
  • the mass ratio of sodium and acetylene black is 85:15:0.
  • the present embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (a), the second The binder is a binder to which calcium ions are added, wherein calcium ions are added by calcium chloride, and the mass ratio of calcium ions to sodium alginate added is 2..25.
  • the present embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (a), the second The binder is a binder to which copper ions are added, wherein copper ions are added by means of copper sulfate, and the mass ratio of the added copper ions to sodium alginate is 1..10.
  • the present embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (a), the second step is adopted.
  • the mass ratio of the binder gum arabic, silicon powder, gum arabic and acetylene black is 85:10:5.
  • the present embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (a), the second step is adopted.
  • the binder is guar gum, the mass ratio of silicon powder, guar gum and acetylene black is 80:10:10; in step (b), the first binder used is sodium carboxymethylcellulose and A mixture of styrene butadiene rubber emulsions.
  • the present embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (a), the second step is adopted.
  • the binder is sodium hyaluronate, the mass ratio of silicon powder, sodium hyaluronate and acetylene black is 75:15:10; in step (b), the first binder used is sodium carboxymethylcellulose and A mixture of styrene butadiene rubber emulsions.
  • the present embodiment provides a microcapsule-type silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (c), graphite and silicon are controlled.
  • the weight ratio of the powder is 4:1.
  • the present embodiment provides a silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (a), sodium alginate is not added, but Add the same amount of sodium carboxymethylcellulose.
  • the present embodiment provides a silicon-carbon composite anode material, which is prepared by the following method, and the preparation steps thereof are basically the same as those in Embodiment 1, except that in step (b), carboxymethyl cellulose is not added. Sodium, but add the same amount of sodium alginate.

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Abstract

本发明公开了一种微胶囊型硅碳复合负极材料，所述负极材料包括集流体，以及由涂覆在所述集流体上的硅碳浆料干燥而形成的硅碳涂层，所述硅碳浆料包括碳质浆料和分散在所述碳质浆料中的硅胶囊粉体，所述碳质浆料包括分散剂和分散在所述分散剂中的碳材料、第一导电剂、第一粘结剂；所述硅胶囊粉体包括硅粉和包覆在所述硅粉表面的第二粘结剂，所述第二粘结剂以及为其包覆的硅粉之间形成微胶囊结构；所述第一粘结剂和所述第二粘结剂不同；本发明的改进的硅碳复合负极材料，具有其循环性能、库伦效率、倍率性能均取得极其优异的效果。

Description

一种微胶囊型硅碳复合负极材料及其制备方法和应用 技术领域
本发明属于锂离子电池电极领域，具体涉及一种微胶囊型硅碳复合负极材料及其制备方法和应用。
背景技术
硅材料具有很高的储锂容量，其理论容量大约4200mAh/g，实际比容量超过3000mAh/g，是极有可能替代石墨材料成为下一代高比能锂电池的重要负极材料。然而，硅材料的应用面临最关键的技术问题有三个，一是硅颗粒在锂离子嵌入和脱出过程中硅材料体积发生剧烈的变化，膨胀率可以达到300％，并由此造成硅颗粒粉化和极片容量迅速下降的问题，二是硅材料的首次库伦效率不高，三是硅表面SEI膜的稳定性差，特别是在体积变化过程中不断破坏和生长，造成严重的锂消耗问题。为了解决上述问题，人们主要从三个方面入手，一是硅材料的修饰和改性，包括硅材料的粒度控制、表面控制以及与碳材料的复合等几个方面，二是选择适合的粘结剂体系，特别是选择具有三维网络型交联结构的粘结剂体系，包括交联型海藻酸盐体系、交联型聚丙烯酰胺体系等，目前这方面的研究也取得了很好的结果，三是优良电解液体系的选择，特别是含有氟代碳酸乙烯酯(FEC)的电解液***显示了很好的性能。
现有技术中，硅材料产业化应用的选择之一是硅碳复合，事实上，硅碳复合的方式有很多种，包括硅材料表面原位生长碳材料，包括无定型碳，碳纳米管和石墨烯等，但这种材料制备过程非常繁杂，碳材料生长过程中容易形成氧化硅和碳化硅，影响硅材料的性能，另一种是硅颗粒和碳材料的机械混合，这种机械混合很容易把二者混合均匀，特别是硅粉体和石墨材料的机械混合已经得到了产业化应用，一般可以在石墨粉体中混10％左右的硅颗粒，用于生产具有超过400mAh/g容量的碳负极片，虽然这种制造方法简单，易于实现，但面临的突出问题是电极的容量衰减快，经过200次左右的循环后，硅材料基本发挥不出应有的性能，对高比能电池的寿命造成很大影响。
针对上述存在的问题，现有技术中进行了一些改进，例如中国发明专利CN103022448A公开了一种锂电池硅碳负极材料的制备方法，包括以下步骤：1)将50～90重量份的微米级硅粉加入球磨罐中，加入溶剂，进行球磨；2)将10～50重量份的天然石墨加入步骤1)球磨好的工业硅粉中，继续球磨；3)对步骤2)球磨好的物质进行干燥处理，并将干燥后的物质研细，制得活性物质；4)称取70～80重量份的所述活性物质、5～20重量份的海藻酸钠和5～20重量份的乙炔黑，加入去离子水，去离子水与海藻酸钠的质量比为1:5～1:1，搅拌均匀后涂在铜箔上，烘干，得到硅碳负极材料。虽然此专利中在一定程度上实现了电极片首次库伦率的提升(70％以上)，但仍然不理想，且长期循环性能也不满足高要求(循环50次时下降很明显)，且对电极片的倍率性能没有任何改善。
发明内容
本发明所要解决的技术问题是克服现有技术的不足，提供一种改进的硅碳复合负极材料，本发明的微胶囊型硅碳复合负极材料具有其循环性能、库伦效率、倍率性能均取得极其优异的效果。
本发明还提供了一种制备微胶囊型硅碳复合负极材料的方法。
本发明还提供了一种微胶囊型硅碳复合负极材料在制备锂离子电池电极片中的应用。
为解决以上技术问题，本发明采取的一种技术方案如下：
一种微胶囊型硅碳复合负极材料，所述负极材料包括集流体，以及由涂覆在所述集流体上的硅碳浆料干燥而形成的硅碳涂层，所述硅碳浆料包括碳质浆料和分散在所述碳质浆料中的硅胶囊粉体，所述碳质浆料包括分散剂和分散在所述分散剂中的碳材料、第一导电剂、第一粘结剂；所述硅胶囊粉体包括硅粉和包覆在所述硅粉表面的第二粘结剂，所述第二粘结剂以及为其包覆的硅粉之间形成微胶囊结构；所述第一粘结剂和所述第二粘结剂不同。
所述微胶囊结构即为第二粘结剂包覆在硅粉表面形成的固体微粒或颗粒等，此处固体颗粒或微粒以硅粉为核，第二粘结剂为外壳包覆在硅粉表面。
根据本发明的一个优选方面，当所述硅胶囊粉体被分散到所述碳质浆料中时，所述第一粘结剂与所述第二粘结剂之间不溶、难溶或微溶。
根据本发明的一个更为优选方面，所述第一粘结剂为羧甲基纤维素钠和/或丁苯橡胶，所述第二粘结剂为选自海藻酸盐、聚丙烯酸盐、***胶、瓜尔豆胶和透明质酸盐中的一种或多种的组合。
根据本发明的一些优选方面，所述第二粘结剂为添加有钙离子和/或铜离子的粘结剂，其中钙离子和/或铜离子占所述第二粘结剂的质量分数为2～15％。其中铜离子和/或钙离子的添加可以使得粘结剂形成的外壳的稳定性和力学性能更好，在一些具体实施方式中，还可以添加其他能够交联粘结剂的成分，以此获得改性的粘结剂，使粘结剂形成的外壳能够具有较强的力学性能和稳定性。更优选地，所述第二粘结剂为添加有钙离子和/或铜离子的粘结剂，其中钙离子和/或铜离子占所述第二粘结剂的质量分数为5～12％。
在本发明的一些具体且优选的实施方式中，在所述硅碳浆料中，所述碳材料和所述硅粉的重量比为2～10︰1。
在本发明的一些具体且优选的实施方式中，所述硅粉、第二粘结剂分别占所述硅胶囊粉体的原料的质量分数为70～95％和2～15％。
在本发明的一些具体且优选的实施方式中，所述碳材料、第一粘结剂、第一导电剂分别占所述碳质浆料的质量分数为90～98％、1～5％和0.5～5％。
在本发明的一些具体实施方式中，所述硅粉为纳米硅和/或微米硅。
在本发明的一些具体实施方式中，所述碳材料为选自天然石墨、人工石墨、热解碳或硬碳材料中的一种或多种的组合。
在本发明的一些具体实施方式中，所述分散剂为水，或，醇类与水的混合溶剂。
在本发明的一些具体实施方式中，所述第一导电剂为选自乙炔黑、Super P、Super S、碳纤维、碳纳米管和石墨烯中的一种或多种的组合。
在本发明的一些具体实施方式中，优选地，所述硅胶囊粉体还包括第二导电剂，所述第二导电剂为选自乙炔黑、Super P、Super S、碳纤维、碳纳米管和石墨烯中的一种或多种的组合。
本发明提供的另一技术方案，一种上述所述的微胶囊型硅碳复合负极材料的制备方法，所述制备方法包括以下步骤：
(a)硅胶囊粉体的制备：将所述硅胶囊粉体的所述硅粉和所述第二粘结剂分散在分散剂中得到硅质浆料，然后将所述硅质浆料烘干，研磨，即得以所述硅粉为核、所述第二粘结剂为外壳的微胶囊结构的所述硅胶囊粉体；其中，在分散剂中加入第二导电剂，或不加；
(b)碳质浆料的制备：将所述碳材料的粉体、第一粘结剂、第一导电剂分散在分散剂中，即得所述碳质浆料；
(c)硅碳浆料的制备：在所述碳质浆料的制备即将完成时、完成时或完成后将步骤(a)制备的所述硅胶囊粉体加入到步骤(b)制备的所述碳质浆料中，混合搅拌，即得所述硅碳浆料；
(d)微胶囊型硅碳复合负极材料的制备：将步骤(c)制备的所述硅碳浆料涂覆在所述集流体上，烘干，即得所述微胶囊型硅碳复合负极材料。
本发明提供的又一技术方案，一种上述所述的微胶囊型硅碳复合负极材料在制备锂离子电池电极片中的应用。
由于以上技术方案的采用，本发明与现有技术相比具有如下优点：
本发明的负极材料中硅粉和碳材料分别置于不同的粘结剂环境中，同时硅粉被第二粘结剂完全包覆形成微胶囊结构，使得硅和碳的活性均得到最大化的利用，实现了电极片的长期循环性能大幅度提高，由原来的200次明显衰减提高到几乎不会衰减，电极片的内阻明显降低，倍率性能大大提高，电极片的机械稳定性明显提高，电极片的首次库伦效率极大提高，因此本发明的硅碳负极材料对发展未来高比能和长寿命锂离子电池具有重要的意义。
具体实施方式
基于现实对高比能锂电池的需求，本发明提出一种具有微胶囊结构的硅碳复合负极材料，具体地讲，就是首先优选适合硅颗粒的粘结剂与硅颗粒一起混合分散，在硅颗粒表面均匀包覆一层与之配伍性好的粘结剂，优选地进一步通过交联技术加强这种粘结剂的稳定性，形成以硅颗粒为核，交联改性后的粘结剂为外壳的微胶囊结构，再基于现代碳质(石墨)浆料 制备基本完成的前后时间，加入硅胶囊粉体，搅拌，使硅胶囊粉体均匀分散在碳质浆料当中，这样就形成了硅在适合硅的粘结剂中，碳在适合碳的粘结剂中(优选这两种不同的粘结剂之间不溶、难溶或微溶，但又没有明显的相界面)，以此形成硅碳浆料，进而将硅碳浆料涂覆在集流体上，干燥，即得微胶囊型硅碳复合负极材料，可加工成锂离子电池用的电极片，这种电极片突出的特点是含有两种不同的粘结剂，保证每一种活性物质在其最适合的粘结剂环境中工作，避免了现有技术中的电极片循环性能差和库伦效率低、倍率性能差的问题，是发展未来高容量长寿命硅碳复合电极的重要技术和途径。
本发明微胶囊结构的硅碳复合负极材料的制备方法，它包括以下步骤：(a)将硅粉(采用常见的锂电池用纳米或微米硅粉)、第二粘结剂、第二导电剂(优选加入，也可不加)分散在分散剂中，搅拌混合得硅质浆料，随后将所述硅质浆料在适当的温度(优选60～90℃)条件下烘干，研磨，即得以所述硅粉为核、所述第二粘结剂为外壳的微胶囊结构的所述硅胶囊粉体；所述第二粘结剂为选自海藻酸盐、聚丙烯酸盐、***胶、瓜尔豆胶和透明质酸盐中的一种或多种组成的混合物；(b)将碳材料的粉体、第一粘结剂、第一导电剂分散在分散剂中，混合搅拌均匀得碳质浆料；所述第一粘结剂选自羧甲基纤维素钠和/或丁苯橡胶；(c)在碳质浆料制备即将完成时、完成时或完成后，加入所述硅胶囊粉体，继续搅拌30分钟左右，即得硅碳浆料；(d)将所得到的硅碳浆料涂敷在集流体上，涂布厚度优选40～200微米，烘干(优选60℃)，即得到微胶囊型硅碳复合负极材料。在制备混合硅胶囊粉体时优选使用富含羧基或羟基的第二粘结剂，有利于硅表面成膜提高材料的首次库伦效率，优选地，所述第二粘结剂为添加有钙离子和/或铜离子的粘结剂，其中钙离子和/或铜离子占所述第二粘结剂的质量分数为2～15％，更优选地，其中钙离子和/或铜离子占所述第二粘结剂的质量分数为5～12％，所述铜离子和/或钙离子通过CaCl 2、CaSO 4、CuCl 2、CuSO 4等形式添加，粘结剂进一步交联改性不仅降低其在碳质浆料中溶解的可能，还可以抑制硅在循环过程中的体积效应，当其与碳质浆料进行混合时，则可以使得硅和碳均处于各自最佳的粘结剂环境中，有利提高电极 片的电性能。第一、第二导电剂均为选自乙炔黑、Super P、Super S、碳纤维、碳纳米管的一种或多种组成的混合物；步骤(a)、(b)中使用的分散剂均可以为水，或，水和醇类溶剂的混合溶剂。其中，碳材料和硅粉之间的重量比控制在2～10︰1，所述硅粉、第二粘结剂分别占所述硅胶囊粉体的质量分数为70～95％、2～15％，优选地，所述硅胶囊粉体中还包括占所述硅胶囊粉体的质量分数为0.01～15％的第二导电剂；所述碳材料、第二粘结剂、第二导电剂分别占所述碳质浆料的质量分数为90～98％、1～5％和0.5～5％。
以下结合具体实施例对上述方案做进一步说明；应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。在以下实施例中，未作特殊说明，所有原料均来自商购。
实施例1
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备而得：
(a)将硅粉(100nm)、海藻酸钠和乙炔黑按照质量比80：15：5分散在水中充分搅拌，得到混合均匀的硅质浆料；硅质浆料在80℃下烘干，充分研磨过筛后即得以所述硅粉为核、所述海藻酸钠为外壳的微胶囊结构的硅胶囊粉体；
(b)将石墨的粉体、羧甲基纤维素钠、丁苯橡胶和乙炔黑按照质量比95：2：1：2分散在水中充分搅拌，得到混合均匀的石墨浆料；
(c)在石墨浆料制备即将完成时，加入所述硅胶囊粉体，控制石墨与硅粉的重量比为3:1，加入完成后继续搅拌30分钟，即得硅碳浆料；
(d)将所得到的硅碳浆料涂敷在集流体上，在60℃下烘干，即得到微胶囊型硅碳复合负极材料。
将所得微胶囊型硅碳复合负极材料制成负极电极片，以锂片作为对电极，组装成2032扣式电池，电解液是1M LiPF 6为导电盐的体积比为1：1：1的EC/DMC/DEC溶液，并加入占电解液的质量分数为10％的FEC作为 添加剂；将组装的电池封口，静置后，在充放电测试仪上恒电流测试电化学性能(其中充放电倍率均为0.2C，电压范围在0.01～1V)。
实施例2
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(a)中，硅粉、海藻酸钠和乙炔黑的质量比为85：15：0。
实施例3
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(a)中，所述第二粘结剂为添加了钙离子的粘结剂，其中，钙离子通过氯化钙的方式加入，加入的钙离子与海藻酸钠的质量比为2︰25。
实施例4
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(a)中，所述第二粘结剂为添加了铜离子的粘结剂，其中，铜离子通过硫酸铜的方式加入，加入的铜离子与海藻酸钠的质量比为1︰10。
实施例5
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(a)中，采用的第二粘结剂***胶，硅粉、***胶和乙炔黑的质量比为85：10：5。
实施例6
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(a)中，采用的第二粘结剂为瓜尔豆胶，硅粉、瓜尔豆胶和乙炔黑的质量比为80：10：10；步骤(b)中，采用的第一粘结剂为羧甲基纤维素钠和丁苯橡胶乳液的混合物。
实施例7
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备 而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(a)中，采用的第二粘结剂为透明质酸钠，硅粉、透明质酸钠和乙炔黑的质量比为75：15：10；步骤(b)中，采用的第一粘结剂为羧甲基纤维素钠和丁苯橡胶乳液的混合物。
实施例8
本实施例提供一种微胶囊型硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(c)中，控制石墨与硅粉体的重量比为4:1。
对比例1
本实施例提供一种硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(a)中，未加入海藻酸钠，但加入等量的羧甲基纤维素钠。
对比例2
本实施例提供一种硅碳复合负极材料，其通过如下方法制备而得，它的制备步骤与实施例1中的基本一致，不同的是：步骤(b)中，未加入羧甲基纤维素钠，但加入等量的海藻酸钠。
性能测试
将上述实施例1-8以及对比例1-2所制得的电极片进行如下性能测试，具体结果参见表1所示。
表1、实施例1-8、对比例1-2中锂离子电池负极片的电化学性能表
Figure PCTCN2018106160-appb-000001
Figure PCTCN2018106160-appb-000002
由上表测试结果可知，这种新型几何结构的微胶囊硅碳复合负极材料制成的电极片的循环性能大大提升，200次循环后，电极片的容量保持率由传统电极片的30％左右上升到接近90％，说明电极片的寿命得到了大幅度提高。不仅如此，微胶囊硅碳复合电极片的倍率性能也显著升高，在10C放电条件下，由传统电极片的30mAh/g左右提升到600mAh/g左右，提高20倍，可见，该发明克服了传统硅碳混合电极片在倍率和循环方面的劣势，电极片的循环性能和倍率性能大大提高。这种新型几何结构的电极片对发展未来高比能和长寿命锂离子电池具有重要的意义。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种微胶囊型硅碳复合负极材料，所述负极材料包括集流体，以及由涂覆在所述集流体上的硅碳浆料干燥而形成的硅碳涂层，其特征在于，所述硅碳浆料包括碳质浆料和分散在所述碳质浆料中的硅胶囊粉体，所述碳质浆料包括分散剂和分散在所述分散剂中的碳材料、第一导电剂、第一粘结剂；所述硅胶囊粉体包括硅粉和包覆在所述硅粉表面的第二粘结剂，所述第二粘结剂以及为其包覆的硅粉之间形成微胶囊结构；所述第一粘结剂和所述第二粘结剂不同。
  2. 根据权利要求1所述的微胶囊型硅碳复合负极材料，其特征在于，当所述硅胶囊粉体被分散到所述碳质浆料中时，所述第一粘结剂与所述第二粘结剂之间不溶、难溶或微溶。
  3. 根据权利要求2所述的微胶囊型硅碳复合负极材料，其特征在于，所述第一粘结剂为羧甲基纤维素钠和/或丁苯橡胶，所述第二粘结剂为选自海藻酸盐、聚丙烯酸盐、***胶、瓜尔豆胶和透明质酸盐中的一种或多种的组合。
  4. 根据权利要求1所述的微胶囊型硅碳复合负极材料，其特征在于，所述第二粘结剂为添加有钙离子和/或铜离子的粘结剂，其中钙离子和/或铜离子占所述第二粘结剂的质量分数为2-15％。
  5. 根据权利要求1所述的微胶囊型硅碳复合负极材料，其特征在于，在所述硅碳浆料中，所述碳材料和所述硅粉的重量比为2～10︰1。
  6. 根据权利要求1所述的微胶囊型硅碳复合负极材料，其特征在于，所述硅粉、第二粘结剂分别占所述硅胶囊粉体的原料的质量分数为70～95％和2～15％，所述碳材料、第一粘结剂、第一导电剂分别占所述碳质浆料的质量分数为90～98％、1～5％和0.5～5％。
  7. 根据权利要求1所述的微胶囊型硅碳复合负极材料，其特征在于，所述硅粉为纳米硅和/或微米硅；所述碳材料为选自天然石墨、人工石墨、热解碳或硬碳材料中的一种或多种的组合；所述分散剂为水，或，醇类与水的混合溶剂；所述第一导电剂为选自乙炔黑、Super P、Super S、碳纤维、碳纳米管和石墨烯中的一种或多种的组合。
  8. 根据权利要求1所述的微胶囊型硅碳复合负极材料，其特征在于，所述硅胶囊粉体还包括第二导电剂，所述第二导电剂为选自乙炔黑、Super P、Super S、碳纤维、碳纳米管和石墨烯中的一种或多种的组合。
  9. 一种权利要求1-8中任一项权利要求所述的微胶囊型硅碳复合负极材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    (a)硅胶囊粉体的制备：将所述硅胶囊粉体的所述硅粉和所述第二粘结剂分散在分散剂中得到硅质浆料，然后将所述硅质浆料烘干，研磨，即得以所述硅粉为核、所述第二粘结剂为外壳的微胶囊结构的所述硅胶囊粉体；其中，在分散剂中加入第二导电剂，或不加；
    (b)碳质浆料的制备：将所述碳材料的粉体、第一粘结剂、第一导电剂分散在分散剂中，即得所述碳质浆料；
    (c)硅碳浆料的制备：在所述碳质浆料的制备即将完成时、完成时或完成后将步骤(a)制备的所述硅胶囊粉体加入到步骤(b)制备的所述碳质浆料中，混合搅拌，即得所述硅碳浆料；
    (d)微胶囊型硅碳复合负极材料的制备：将步骤(c)制备的所述硅碳浆料涂覆在所述集流体上，烘干，即得所述微胶囊型硅碳复合负极材料。
  10. 一种权利要求1-8中任一项权利要求所述的微胶囊型硅碳复合负极材料在制备锂离子电池电极片中的应用。
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