WO2019114556A1 - 一种硅基负极材料、其制备方法及在锂离子电池的用途 - Google Patents
一种硅基负极材料、其制备方法及在锂离子电池的用途 Download PDFInfo
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Definitions
- the present invention relates to the field of lithium ion batteries, and relates to a silicon-based anode material, a preparation method thereof and use thereof, for example, to a silicon-based anode material, a preparation method thereof and use thereof in a lithium ion battery.
- the performance indexes such as energy density and power density of lithium-ion batteries need to be further improved.
- the conventional graphite carbon anode material has a limited specific capacity (372 mAh/g), which has been difficult to meet the demand of high energy density batteries.
- the anode material with high specific capacity has become the focus of current research.
- Silicon based materials have received much attention due to their theoretical specific capacity of up to 4200 mAh/g.
- the silicon negative electrode material has low reversible capacity and poor cycle stability.
- researchers have conducted a large number of experimental studies, such as conductive polymer coating, carbon coating, compounding with metal oxides, nanocrystallization and porosity.
- the patent CN 106229495 A discloses a conductive polymer-coated silicon-based anode material and a preparation method thereof.
- the technical point is that the conductive polymer (polythiophene, polyaniline, polypyrrole) is coated on the silicon-based material by in-situ polymerization, and sodium alginate is added to enhance the stability, and the expansion of the three-dimensional network structure buffer silicon material is constructed, but
- the conductive polymer coated by the method has low conductivity, unstable electrical conductivity, easy to dedoping and lose conductivity, resulting in a decrease in material cycle performance, and the in-situ polymerization preparation process used is complicated.
- CN 105186003 A discloses a method for preparing a high-capacity lithium ion battery anode material, which comprises dispersing a polymer, a conductive agent and a non-carbon anode material into a suitable solvent to form a uniform emulsion, and then performing freezing or spray drying to obtain A uniform black powder material is dried under vacuum to obtain a conductive polymer-coated high-capacity negative electrode material, and the polymer is used to improve the volume change of the non-carbon negative electrode during the cycle, but the material prepared by the method, the conductive agent is dispersed in the active Around the material, the connection with the active material is lost during the cycle, and the strength of the polymer is low, and the expansion of the non-carbon negative electrode material is not effectively improved.
- the purpose of the application is to provide a silicon-based anode material, a preparation method thereof and the use thereof in a lithium ion battery.
- the silicon-based anode material of the present application has excellent electrochemical cycle and inhibiting expansion performance, and can prolong the service life of the lithium ion battery.
- the preparation method of the present application is simple, effective, low in cost, and easy to realize industrialization and green environmental protection in the production process.
- the present application provides a silicon-based anode material, the anode material comprising a silicon-based active material, and a composite layer composed of a flexible polymer and a conductive material coated on the surface of the silicon-based active material, wherein
- the conductive material contains flake graphite and a nanocarbon-based material.
- the flake graphite is completely adhered to the surface of the silicon-based active material, the high-strength flexible polymer is coated on the surface of the silicon-based active material and the flake graphite, and the nano-carbon material fills the surface of the silicon-based active material.
- the combination of the above three materials constitutes a composite layer, and the combination of the above three substances can more effectively suppress the expansion of the silicon-based material, and the coated silicon-based negative electrode material has high conductivity.
- the conductivity is stable. Therefore, the silicon-based anode material provided by the present application is very suitable for use in a lithium ion battery and has excellent cycle expansion properties.
- the silicon-based active material has a particle diameter of 0.5 to 100 ⁇ m, for example, 0.5 ⁇ m, 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, 20 ⁇ m, 35 ⁇ m, 50 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m or 100 ⁇ m or the like.
- the composite layer has a thickness of 10-100 nm, such as 10 nm, 20 nm, 30 nm, 45 nm, 60 nm, 70 nm, 80 nm, 85 nm, 90 nm, 95 nm or 100 nm, and the like.
- the silicon-based active material includes any one of Si, SiO x or a silicon alloy or a combination of at least two, wherein 0 ⁇ x ⁇ 2.
- silicon-based active materials it is not limited to the above-exemplified silicon-based active materials, and other silicon-based active materials such as carbon-coated silicon oxides which are commonly used in the art can also be used in the present application.
- the flexible polymer is a natural flexible polymer and/or a synthetic flexible polymer.
- natural flexible polymer and/or synthetic flexible polymer means: a natural flexible polymer, a synthetic flexible polymer, a natural flexible polymer, and a synthetic flexibility. a mixture of polymers.
- the flexible polymer is a polyolefin and its derivatives, polyvinyl alcohol and its derivatives, polyacrylic acid and its derivatives, polyamide and its derivatives, carboxymethyl cellulose and its derivatives, or Any one or a combination of at least two of alginic acid and derivatives thereof, typical but non-limiting examples of which are: a combination of a polyolefin and a polyvinyl alcohol, a combination of polyvinyl alcohol and carboxymethyl cellulose, a carboxy group Combination of methylcellulose and alginic acid, combination of polyamide and carboxymethylcellulose derivatives, combination of polyolefin, polyolefin derivative and polyacrylic acid, polyvinyl alcohol, polyamide derivative and alginic acid A combination of polyolefin, polyvinyl alcohol, a derivative of polyacrylic acid, a combination of polyamide and alginic acid, and the like.
- the flexible polymer is a combination of a polyolefin and its derivatives, a polyolefin and derivatives thereof, and alginic acid and derivatives thereof.
- the flexible polymer has a weight average molecular weight of 2000-1000000, such as 2000, 5000, 10000, 15000, 20000, 30000, 40,000, 50000, 60,000, 75,000, 100,000, 200,000, 300,000, 350,000, 400,000, 500,000. , 600000, 650,000, 700,000, 800,000, 900,000 or 1000000, etc., optionally 100000-500000.
- the flexible polymer contains a thermal cross-linking functional group (also referred to as a heat-crosslinkable functional group), and the thermal cross-linking functional group includes an epoxy group, a carboxyl group, Any one or a combination of at least two of a hydroxyl group, an amino group, a double bond or a hydrazone bond.
- a thermal cross-linking functional group also referred to as a heat-crosslinkable functional group
- the flake graphene is natural flake graphite and/or artificial flake graphite.
- the conductive material is a combination of flake graphite and nano carbon materials.
- the two materials can be better combined with the silicon-based composite material to inhibit the expansion of the silicon-based material, thereby further improving the electrical conductivity and the electrical conductivity stability.
- natural flake graphite and/or artificial flake graphite means either natural flake graphite or artificial flake graphite, or a mixture of natural flake graphite and artificial flake graphite.
- the nanocarbon-based material comprises any one of conductive graphite, graphene, carbon nanotubes or carbon nanofibers or a combination of at least two.
- the mass percentage of the flexible polymer is 0-10% and does not include 0, such as 0.5%, 1%, 1.5%, 2%, based on 100% of the total mass of the silicon-based active material. 3%, 4%, 5%, 6.5%, 8%, 9% or 10%, etc., optionally 3-7%.
- the mass percentage of the flake graphite is 0-20%, and does not include 0, such as 0.5%, 1%, 3%, 3.5%, based on 100% of the total mass of the silicon-based active material. 5%, 6%, 8%, 10%, 12%, 13%, 15%, 16%, 18% or 20%, etc., optionally 5-10%.
- the nanocarbon material has a mass percentage of 0-5% and does not include 0, such as 0.5%, 1%, 2%, 2.5, based on 100% of the total mass of the silicon-based active material. %, 3%, 4% or 5%, etc., optionally 1-3%.
- the present application provides a method for preparing a silicon-based anode material according to the first aspect, the method comprising the steps of:
- the negative electrode material precursor is subjected to heat treatment to obtain a silicon-based negative electrode material.
- the method of the present application gradually coats the surface of the silicon-based active material by dispersing the silicon-based active material in a supersaturated solution of a flexible polymer in which the flake graphite and the nanocarbon-based material are dispersed, and utilizing the characteristics of the super-saturated solution.
- the flake graphite and the conductive material dispersed in the solution are attached to the surface of the silicon-based active material by the pulling and binding of the polymer.
- the silicon-based negative electrode material prepared by the method of the present application utilizes the very good fit of the flake graphite and the effect of the nano-carbon material to fill the void, so that the structure of the coated material is stable, the conductivity is high, and the conductivity is stable. .
- the flexible polymer of step (1) contains a thermal cross-linking functional group including an epoxy group, a carboxyl group, a hydroxyl group, an amino group, a double bond or Any one of the ⁇ keys or a combination of at least two.
- the flexible polymer contains a large amount of crosslinkable functional groups, which undergo cross-linking in the subsequent heat treatment to enhance the strength of the coating layer to inhibit the expansion of the material during the cycle.
- the solvent in the step (1) is water, methanol, ethanol, polypyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N,N-dimethylacetamide, N,N- Any one or a combination of at least two of dimethylformamide, n-hexane or halogenated hydrocarbon.
- step (1) after dissolving the flexible polymer in the solvent, stirring is performed at 25-100 ° C, for example, 25 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C or 100 ° C and so on.
- the conductive material comprising the flake graphite and the nano carbon material in the step (2) is a combination of a flake graphite and a nano carbon material.
- the two materials can be better combined with the silicon-based composite material to inhibit the expansion of the silicon-based material, thereby further improving the electrical conductivity and the electrical conductivity stability.
- step (2) adding a conductive material comprising flake graphite and a nanocarbon-based material to the flexible polymer solution, stirring is continued for 2-4 h, such as 2 h, 2.5 h, 3 h, 3.5 h or 4 h, and the like.
- the anti-solvent in the step (3) is a poor solvent of the flexible polymer, and is selected from the group consisting of methanol, ethanol, polypyrrolidone, isopropanol, acetone, petroleum ether, tetrahydrofuran, ethyl acetate, N, N- Any one or a combination of at least two of dimethylacetamide, N,N-dimethylformamide, n-hexane or a halogenated hydrocarbon.
- the stirring time in the step (3) is 1-2 h, such as 1 h, 1.2 h, 1.5 h, 1.6 h, 1.8 h or 2 h, and the like.
- the step (4) is carried out by adding a silicon-based active material to the super-saturated mixed coating liquid, followed by stirring at 25-80 ° C for 2-4 h.
- the stirring temperature is, for example, 25 ° C, 30 ° C, 40 ° C, 45 ° C, 50 ° C, 60 ° C, 70 ° C or 80 ° C, etc.; the stirring time is, for example, 2 h, 2.5 h, 3 h, 3.2 h, 3.5 h or 4 h, and the like.
- the manner of separating in the step (4) includes any one of normal pressure filtration, vacuum filtration or centrifugation, but is not limited to the separation methods listed above, and other separation methods commonly used in the art to achieve the same effect. It can also be used in this application.
- the temperature of the heat treatment in the step (5) is 100-400 ° C, such as 100 ° C, 125 ° C, 150 ° C, 170 ° C, 200 ° C, 220 ° C, 240 ° C, 260 ° C, 300 ° C, 350 ° C or 400 ° C, etc., can be selected from 150-250 ° C.
- the heat treatment time in the step (5) is 2-12 h, for example, 2 h, 4 h, 5 h, 6.5 h, 8 h, 10 h, 11 h or 12 h, and the like.
- the anode material precursor obtained in the step (4) is a silicon-based material which is co-coated with flake graphite, a nanocarbon-based material and a flexible polymer, and after the heat treatment in the step (5), the flexible polymer
- the cross-linking of the crosslinkable groups enhances the strength of the coating to inhibit expansion of the material during cycling.
- the method includes the following steps:
- the anti-solvent is a poor solvent of a flexible polymer containing a thermally crosslinked functional group.
- the present application provides a negative electrode comprising the silicon-based negative electrode material of the first aspect.
- the present application provides a lithium ion battery comprising the negative electrode of the third aspect.
- the present application utilizes the characteristics of a polymer supersaturated solution to firmly adhere the flake graphite to the surface of the silicon-based active material by the pulling and binding of the polymer while the polymer is precipitating and coating the silicon-based active material. And the nano-carbon material is firmly filled in the void, and the electrical connection is maintained during the cyclic expansion of the silicon-based active material, and the flake graphite completely bonded to the surface of the silicon-based active material is coated and coated on the surface of the silicon-based active material.
- the combination of the strength polymer coating and the nano-carbon material filled in the void can effectively inhibit the expansion of the silicon-based active material, and at the same time, the prepared package is obtained due to the bonding of the flake graphite and the void filling of the nano-carbon material.
- the coated silicon-based anode material has excellent performance and is very suitable for use in lithium ion batteries. Its conductivity is high and its conductivity is stable. It is significantly improved by the combination of flake graphite coating, flexible polymer coating and nano-carbon material filling.
- the silicon-based active material inhibits the cyclic expansion property and prolongs the service life of the lithium ion battery.
- Fig. 1 is a graph showing the 50-cycle cycle capacity retention ratio of a battery made of a silicon-based negative electrode material for a lithium ion battery obtained in Example 3 of the present application.
- the embodiment provides a silicon-based anode material for a lithium ion battery, and the silicon-based anode material is prepared by the following method:
- the embodiment provides a silicon-based anode material for a lithium ion battery, and the silicon-based anode material is prepared by the following method:
- the embodiment provides a silicon-based anode material for a lithium ion battery, and the silicon-based anode material is prepared by the following method:
- the 50-cycle cycle capacity retention rate of the battery is 91.2%.
- the embodiment provides a silicon-based anode material for a lithium ion battery, and the silicon-based anode material is prepared by the following method:
- the negative electrode materials prepared in Examples 1-6 were applied to lithium ion batteries, numbered SI-1, SI-2, SI-3, SI-4, 8I-5, and SI-6, respectively.
- the slurry was arranged in a ratio of 92:2:2:2:2, uniformly coated and dried on a copper foil to form a negative electrode tab, and assembled into a button cell in an argon atmosphere glove box, and the separator used was polypropylene.
- the microporous membrane, the electrolyte used was 1 mol/L of lithium hexafluorophosphate (the solvent was a mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate), and the counter electrode used was a lithium metal sheet.
- the above four batteries were cycled for 50 weeks, with a voltage range of 0.005 V to 1.5 V and a current density of 50 mA/g. After the cycle test, the capacity retention rate was calculated, and the lithium ion battery was disassembled, and the thickness of the negative electrode tab was measured.
- the 50-cycle cycle capacity retention rate the 50th cycle cycle discharge capacity / the first cycle discharge capacity * 100%
- the results are shown in Table 1
- the negative electrode piece thickness 50 weeks expansion ratio (thickness after the 50th cycle - The thickness of the uncharged pole piece) / the thickness of the uncharged pole piece * 100%, and the results are shown in Table 1.
- Table 1 50-week cycle capacity retention rate and pole piece expansion ratio of each battery
- SI-2 90.7 38.5 SI-3 91.2 37.7 SI-4 90.8 37.9 SI-5 89.3 39.5 SI-6 90.1 38.3 Ref 85.6 45.4
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Abstract
Description
编号 | 50周循环容量保持率(%) | 50周循环极片膨胀率(%) |
SI-1 | 90.3 | 39.2 |
SI-2 | 90.7 | 38.5 |
SI-3 | 91.2 | 37.7 |
SI-4 | 90.8 | 37.9 |
SI-5 | 89.3 | 39.5 |
SI-6 | 90.1 | 38.3 |
Ref | 85.6 | 45.4 |
Claims (14)
- 一种硅基负极材料,其中,所述负极材料包括硅基活性物质,以及包覆在所述硅基活性物质表面的由柔性聚合物和导电材料构成的复合层;所述导电材料中包含鳞片石墨和纳米碳类材料。
- 根据权利要求1所述的负极材料,其中,所述硅基活性物质的粒径在0.5-100μm。
- 根据权利要求1所述的负极材料,其中,所述复合层的厚度在10-100nm。
- 根据权利要求1所述的负极材料,其中,所述硅基活性物质包括Si、SiO x或硅合金中的任意一种或至少两种的组合,其中0<x≤2;可选地,所述柔性聚合物为天然的柔性聚合物和/或合成的柔性聚合物;可选地,所述柔性聚合物为聚烯烃及其衍生物,聚乙烯醇及其衍生物,聚丙烯酸及其衍生物,聚酰胺及其衍生物,羧甲基纤维素及其衍生物,或海藻酸及其衍生物中的任意一种或至少两种的组合,可选为聚烯烃及其衍生物、聚烯烃及其衍生物与海藻酸及其衍生物的组合;可选地,所述柔性聚合物的重均分子量为2000-1000000,可选为100000-500000。
- 根据权利要求1-4任一项所述的负极材料,其特征在于,所述柔性聚合物上含有热交联型官能团,所述交联型官能团包括环氧基、羧基、羟基、氨基、双键或叁键中的任意一种或至少两种的组合。
- 根据权利要求1-5任一项所述的负极材料,其中,所述鳞片石墨为天然鳞片石墨和/或人造鳞片石墨;优选地,所述导电材料为鳞片石墨与纳米碳类材料的组合;可选地,所述纳米碳类材料包括导电石墨、石墨烯、碳纳米管或碳纳米纤 维中的任意一种或至少两种的组合。
- 根据权利要求1-6任一项所述的负极材料,其中,以所述硅基活性物质的总质量为100%计,所述柔性聚合物的质量百分比为0-10%且不包含0,可选为3-7%;可选地,以所述硅基活性物质的总质量为100%计,所述鳞片石墨的质量百分比为0-20%,且不包含0,可选为5-10%;可选地,以所述硅基活性物质的总质量为100%计,所述纳米碳类材料的质量百分比为0-5%,且不包含0,可选为1-3%。
- 如权利要求1-7任一项所述的硅基负极材料的制备方法,其中,所述方法包括以下步骤:(1)将柔性聚合物溶解于溶剂中,得到柔性聚合物溶液;(2)在搅拌的条件下,向柔性聚合物溶液中加入包含鳞片石墨和纳米碳类材料的导电材料,得到混合包覆液;(3)向混合包覆液中加入反溶剂,搅拌,得到过饱和化后的混合包覆液;(4)在搅拌的条件下,向过饱和化后的混合包覆液中加入硅基活性物质,搅拌,分离,得到负极材料前驱体;(5)对负极材料前驱体进行热处理,得到硅基负极材料。
- 根据权利要求8所述的方法,其中,步骤(2)所述包含鳞片石墨和纳米碳类材料的导电材料为:鳞片石墨和纳米碳类材料的组合。
- 根据权利要求8所述的方法,其中,步骤(1)所述柔性聚合物上含有热交联型官能团,所述热交联型官能团包括环氧基、羧基、羟基、氨基、双键或叁键中的任意一种或至少两种的组合。
- 根据权利要求8所述的方法,其中,步骤(1)所述溶剂为水、甲醇、 乙醇、聚吡咯烷酮、异丙醇、丙酮、石油醚、四氢呋喃、乙酸乙酯、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、正己烷或卤代烃中的任意一种或至少两种的组合;可选地,步骤(1)将柔性聚合物溶解于溶剂之后,在25-100℃的条件下进行搅拌;可选地,步骤(2)向柔性聚合物溶液中加入包含鳞片石墨和纳米碳材料的导电材料之后,继续搅拌2-4h;可选地,步骤(3)所述反溶剂为柔性聚合物的不良溶剂,且选自甲醇、乙醇、聚吡咯烷酮、异丙醇、丙酮、石油醚、四氢呋喃、乙酸乙酯、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、正己烷或卤代烃中的任意一种或至少两种的组合;可选地,步骤(3)所述搅拌的时间为1-2h;可选地,步骤(4)向过饱和化后的混合包覆液中加入硅基活性物质之后,于25-80℃搅拌2-4h;可选地,步骤(4)所述分离的方式包括常压过滤、减压过滤或离心中的任意一种;可选地,步骤(5)所述热处理的温度为100-400℃,可选为150-250℃;可选地,步骤(5)所述热处理的时间为2-12h。
- 根据权利要求8-11任一项所述的方法,其中,所述方法包括以下步骤:(1)将含有热交联型官能团的柔性聚合物溶解于溶剂中,在25-100℃的条件下搅拌,得到柔性聚合物溶液;(2)在搅拌的条件下,向柔性聚合物溶液中加入鳞片石墨和纳米碳类材 料,加入完成后继续搅拌2-4h,得到混合包覆液;(3)向混合包覆液中加入反溶剂,搅拌1-2h,得到过饱和化后的混合包覆液;(4)在搅拌的条件下,向过饱和化后的混合包覆液中加入硅基活性物质,在25-80℃搅拌2-4h,分离,得到负极材料前驱体;(5)对负极材料前驱体于150-250℃热处理2-12h,得到硅基负极材料;其中,所述反溶剂为含有热交联型官能团的柔性聚合物的不良溶剂。
- 一种负极,其中,所述负极包含权利要求1-7任一项所述的硅基负极材料。
- 一种锂离子电池,其中,所述锂离子电池包含权利要求13所述的负极。
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WO2021066458A1 (ko) * | 2019-09-30 | 2021-04-08 | 주식회사 엘지화학 | 복합 음극 활물질, 이의 제조방법, 및 이를 포함하는 음극 |
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Publication number | Publication date |
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JP6928101B2 (ja) | 2021-09-01 |
JP2021182554A (ja) | 2021-11-25 |
EP3726630A1 (en) | 2020-10-21 |
EP3726630A4 (en) | 2021-09-01 |
KR20200092370A (ko) | 2020-08-03 |
US20200280061A1 (en) | 2020-09-03 |
JP2020510960A (ja) | 2020-04-09 |
KR102480641B1 (ko) | 2022-12-22 |
KR20230008225A (ko) | 2023-01-13 |
CN113594455B (zh) | 2023-03-24 |
JP7175355B2 (ja) | 2022-11-18 |
US11515530B2 (en) | 2022-11-29 |
CN113594455A (zh) | 2021-11-02 |
HUE062638T2 (hu) | 2023-11-28 |
EP3726630B1 (en) | 2023-06-28 |
CN108054368B (zh) | 2020-08-11 |
PL3726630T3 (pl) | 2023-12-04 |
KR102547081B1 (ko) | 2023-06-23 |
CN108054368A (zh) | 2018-05-18 |
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