WO2021057765A1 - Carbon-oxide electrolyte-coated battery negative electrode material and preparation method therefor - Google Patents

Carbon-oxide electrolyte-coated battery negative electrode material and preparation method therefor Download PDF

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WO2021057765A1
WO2021057765A1 PCT/CN2020/117016 CN2020117016W WO2021057765A1 WO 2021057765 A1 WO2021057765 A1 WO 2021057765A1 CN 2020117016 W CN2020117016 W CN 2020117016W WO 2021057765 A1 WO2021057765 A1 WO 2021057765A1
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carbon
negative electrode
electrode material
battery negative
oxide electrolyte
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Chinese (zh)
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谭迎宾
李铮铮
王婧洁
杨兵
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宝山钢铁股份有限公司
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Definitions

  • the present invention proposes a carbon-oxide electrolyte-coated battery negative electrode material, which includes: a battery negative electrode material as a core, the battery negative electrode material is coated with a carbon-oxide electrolyte layer, wherein, Carbon coating helps to improve the conductivity of battery anode materials (especially silicon carbon anodes), and oxide electrolytes can provide lithium ion channels to effectively improve the lithium ion conductivity of battery anode materials.
  • the oxide electrolyte particles are 300 nm.
  • the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:

Abstract

Disclosed is a carbon-oxide electrolyte-coated battery negative electrode material, comprising: a battery negative electrode material that acts as a core, wherein a carbon-oxide electrolyte layer coats the outside of the battery negative electrode material. Additionally, further disclosed is a preparation method for the foregoing carbon-oxide electrolyte-coated battery negative electrode material, comprising the steps of: mixing a battery negative electrode material, carbon source organic matter and nanoscale oxide electrolyte particles by means of ball milling; and performing high-temperature calcination so as to obtain the carbon-oxide electrolyte-coated battery negative electrode material. The foregoing battery negative electrode material can overcome defects in the prior art, has relatively high conductivity and a lithium ion conductivity, and can exhibit a high discharge capacity, perfect rate performance and a long cycle performance when applied to a solid-state lithium ion battery negative electrode.

Description

一种碳-氧化物电解质包覆的电池负极材料及其制备方法Battery negative electrode material coated with carbon-oxide electrolyte and preparation method thereof 技术领域Technical field
本发明涉及一种电池材料及其制备方法，尤其涉及一种电池负极材料及其制备方法。The invention relates to a battery material and a preparation method thereof, in particular to a battery negative electrode material and a preparation method thereof.
背景技术Background technique
现在能源问题日益突出，开发和利用新型储能装置成为人们研究重点。锂离子电池具有高的比能量、长的循环寿命、环境友好等优点，其已经在电子设备、电动汽车等领域得到广泛应用。Now that energy issues are becoming increasingly prominent, the development and utilization of new energy storage devices has become the focus of research. Lithium-ion batteries have the advantages of high specific energy, long cycle life, environmental friendliness, etc., and they have been widely used in electronic equipment, electric vehicles and other fields.
然而，现在的常用的锂离子电池一般采用有机液态电解液，而该体系的有机液态电解液易燃易爆，因而，会给电池带来严重的安全隐患。为了解决安全问题，固态电池应运而生，其通过采用固态电解质替代传统有机电解液，从而解决电池安全性问题，然而，目前的负极材料导电性以及放电容量越来越难以满足目前的使用需要。However, current commonly used lithium-ion batteries generally use organic liquid electrolyte, and the organic liquid electrolyte of this system is flammable and explosive, and therefore, it will bring serious safety hazards to the battery. In order to solve the safety problem, solid-state batteries have emerged, which use solid electrolytes instead of traditional organic electrolytes to solve battery safety problems. However, the current conductivity and discharge capacity of negative electrode materials are increasingly difficult to meet current use needs.
基于此，期望获得一种电池负极材料，其可以克服现有技术的不足，该电池负极材料具有较高的导电性以及锂离子电导率，并且在应用于固态锂离子电池负极时，可以展现出高的放电容量，完美的倍率性能和长的循环性能。Based on this, it is desired to obtain a battery negative electrode material that can overcome the shortcomings of the prior art. The battery negative electrode material has high conductivity and lithium ion conductivity, and when applied to the solid state lithium ion battery negative electrode, it can exhibit High discharge capacity, perfect rate performance and long cycle performance.
发明内容Summary of the invention
本发明的目的之一在于提供一种碳-氧化物电解质包覆的电池负极材料，该电池负极材料可以克服现有技术的不足，其具有较高的导电性以及锂离子电导率，并且在应用于固态锂离子电池负极时，其可以展现出高的放电容量、完美的倍率性能和长的循环性能。One of the objectives of the present invention is to provide a battery negative electrode material coated with carbon-oxide electrolyte, which can overcome the shortcomings of the prior art, has high conductivity and lithium ion conductivity, and is used in When used as the negative electrode of a solid-state lithium-ion battery, it can exhibit high discharge capacity, perfect rate performance and long cycle performance.
为了实现上述目的，本发明提出了一种碳-氧化物电解质包覆的电池负极材料，其包括：作为芯部的电池负极材料，电池负极材料外包覆有碳-氧化物电解质层，其中，碳包覆有助于改善电池负极材料(特别是硅碳负极)的导电性，而氧化物电解质可以提供锂离子通道从而有效地改善电池负极材料的锂离 子电导率。In order to achieve the above object, the present invention proposes a carbon-oxide electrolyte-coated battery negative electrode material, which includes: a battery negative electrode material as a core, the battery negative electrode material is coated with a carbon-oxide electrolyte layer, wherein, Carbon coating helps to improve the conductivity of battery anode materials (especially silicon carbon anodes), and oxide electrolytes can provide lithium ion channels to effectively improve the lithium ion conductivity of battery anode materials.
进一步地，在本发明所述的碳-氧化物电解质包覆的电池负极材料中，电池负极材料包括：硅碳、石墨、软碳、硬碳的至少其中之一。Further, in the battery negative electrode material coated with carbon-oxide electrolyte of the present invention, the battery negative electrode material includes at least one of silicon carbon, graphite, soft carbon, and hard carbon.
进一步地，在本发明所述的碳-氧化物电解质包覆的电池负极材料中，碳-氧化物电解质层中的氧化物电解质包括：Li 7La 3Zr 2O 12，0.2Al-Li 7La 3Zr 2O 12，Ba-Sb-Li 7La 3Zr 2O 12，Ge-Li 7La 3Zr 2O 12，Li 6.75La 3Zr 1.75Ta 0.25O 12，Li 6.75La 3Zr 1.75Nb 0.25O 12的至少其中之一。 Further, in the carbon-oxide electrolyte coated battery negative electrode material of the present invention, the oxide electrolyte in the carbon-oxide electrolyte layer includes: Li 7 La 3 Zr 2 O 12 , 0.2Al-Li 7 La 3 Zr 2 O 12 , Ba-Sb-Li 7 La 3 Zr 2 O 12 , Ge-Li 7 La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 O At least one of 12.
需要说明的是，在本发明所述的技术方案中，Li 7La 3Zr 2O 12以下简称LLZO，0.2Al-Li 7La 3Zr 2O 12以下简称LLZAO，Li 6.75La 3Zr 1.75Ta 0.25O 12以下简称LLZTO，Li 6.75La 3Zr 1.75Nb 0.25O 12以下简称LLZNO。 It should be noted that in the technical scheme of the present invention, Li 7 La 3 Zr 2 O 12 is hereinafter referred to as LLZO, 0.2Al-Li 7 La 3 Zr 2 O 12 is hereinafter referred to as LLZAO, and Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 is hereinafter referred to as LLZTO, and Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 is hereinafter referred to as LLZNO.
相应地，本发明的另一目的在于提供一种上述的碳-氧化物电解质包覆的电池负极材料的制备方法，该制备方法所获得的电池负极材料具有较高的导电性以及锂离子电导率。Correspondingly, another object of the present invention is to provide a method for preparing the above-mentioned carbon-oxide electrolyte-coated battery negative electrode material. The battery negative electrode material obtained by the preparation method has high conductivity and lithium ion conductivity. .
为了实现上述目的，本发明提出了一种上述的碳-氧化物电解质包覆的电池负极材料的制备方法，其包括步骤：In order to achieve the above-mentioned objective, the present invention proposes a method for preparing the above-mentioned carbon-oxide electrolyte-coated battery negative electrode material, which includes the steps:
将电池负极材料、碳源有机物和纳米级别的氧化物电解质颗粒通过球磨进行混料；然后进行高温煅烧，以得到碳-氧化物电解质包覆的电池负极材料。碳源有机物提供碳-氧化物电解质层中的碳，氧化物电解质颗粒最终形成碳-氧化物电解质层中的氧化物电解质，且成分与氧化物电解质相同。通过球磨将电池负极材料、碳源有机物和纳米级别的氧化物电解质颗粒混合均匀，避免团聚现象，再通过高温煅烧使碳源有机物碳化，并使氧化物电解质包覆在电池负极材料表面。The battery negative electrode material, carbon source organic matter and nano-level oxide electrolyte particles are mixed through ball milling; then high-temperature calcination is performed to obtain a battery negative electrode material coated with carbon-oxide electrolyte. The carbon source organic matter provides carbon in the carbon-oxide electrolyte layer, and the oxide electrolyte particles finally form the oxide electrolyte in the carbon-oxide electrolyte layer, and the composition is the same as the oxide electrolyte. The battery negative electrode material, carbon source organic matter and nano-scale oxide electrolyte particles are uniformly mixed by ball milling to avoid agglomeration, and then the carbon source organic matter is carbonized by high-temperature calcination, and the oxide electrolyte is coated on the surface of the battery negative electrode material.
进一步地，在本发明所述的制备方法中，碳源有机物包括：聚环氧乙烯，聚乙二醇，蔗糖，葡萄糖、聚吡咯烷酮，聚四氟乙烯，聚氧化乙烯，聚丙烯酸酯，聚氨酯，纤维素，淀粉，氨基酸，三聚氰胺，双氰胺，酚醛树脂，环氧树脂中的至少其中之一。Further, in the preparation method of the present invention, the carbon source organic matter includes: polyethylene oxide, polyethylene glycol, sucrose, glucose, polypyrrolidone, polytetrafluoroethylene, polyethylene oxide, polyacrylate, polyurethane, At least one of cellulose, starch, amino acid, melamine, dicyandiamide, phenol resin, and epoxy resin.
进一步地，在本发明所述的制备方法中，氧化物电解质颗粒的大小在500nm以下，以保证数量充足的导锂离子通道，从而有助于改善电池负极材料的锂离子电导率。Further, in the preparation method of the present invention, the size of the oxide electrolyte particles is below 500 nm to ensure a sufficient number of conductive lithium ion channels, thereby helping to improve the lithium ion conductivity of the battery negative electrode material.
进一步地，在本发明所述的制备方法中，进行球磨的工艺参数满足下述各 项：Further, in the preparation method of the present invention, the process parameters for ball milling satisfy the following items:
球磨速率为100-600rpm；The ball milling speed is 100-600rpm;
球磨时间为1-24h；Ball milling time is 1-24h;
球料比为1-100。The ball-to-material ratio is 1-100.
球磨满足上述各项工艺参数，使得在保证电池负极材料不受破坏的前提下，电池负极材料、碳源有机物和纳米级别的氧化物电解质颗粒混合均匀。Ball milling meets the above-mentioned process parameters, so that the battery negative electrode material, carbon source organic matter and nano-level oxide electrolyte particles are uniformly mixed under the premise of ensuring that the battery negative electrode material is not damaged.
需要说明的是，在本发明所述的技术方案中，球料比是指小球的质量与电池负极材料、碳源有机物和纳米级别的氧化物电解质颗粒的总和的质量比。It should be noted that in the technical solution of the present invention, the ball-to-material ratio refers to the mass ratio of the mass of the pellets to the sum of the battery negative electrode material, carbon source organic matter, and nano-scale oxide electrolyte particles.
进一步地，在本发明所述的制备方法中，煅烧温度为500-900℃，低于500℃，碳源有机物碳化不充分，高于900℃，易出现副反应。Further, in the preparation method of the present invention, the calcination temperature is 500-900°C, lower than 500°C, carbon source organic matter is insufficiently carbonized, and higher than 900°C, side reactions are prone to occur.
进一步地，在本发明所述的制备方法中，煅烧的保护气氛为氮气、氩气、氦气和氨气的至少其中之一，从而避免碳和负极材料转化为二氧化碳逸出等氧化反应。Further, in the preparation method of the present invention, the protective atmosphere for calcination is at least one of nitrogen, argon, helium, and ammonia, so as to avoid oxidation reactions such as carbon and negative electrode materials being converted into carbon dioxide and escaping.
进一步地，在本发明所述的制备方法中，煅烧步骤包括以0.5-20℃/min的速度升温到煅烧温度，升温速率太慢，煅烧时间太长，导致成本太高，升温速率太快，不利于碳化完全，保温0.5-6h，保温时间太短，碳源有机物碳化不充分，保温时间太长，不利于生产效率的提高。Further, in the preparation method of the present invention, the calcination step includes heating up to the calcination temperature at a rate of 0.5-20°C/min, the heating rate is too slow, and the calcination time is too long, resulting in too high cost and too fast heating rate. It is not conducive to complete carbonization, the heat preservation time is 0.5-6h, the heat preservation time is too short, the carbon source organic matter is not sufficiently carbonized, and the heat preservation time is too long, which is not conducive to the improvement of production efficiency.
进一步地，在本发明所述的制备方法中，将电池负极材料、碳源有机物和氧化物电解质颗粒按照(70-95):(5-20):(5-15)的质量份数比例进行混料，从而使碳-氧化物电解质包覆的电池负极材料兼顾充放电容量、导电性、锂离子电导率等方面的性能。Further, in the preparation method of the present invention, the battery negative electrode material, carbon source organic matter and oxide electrolyte particles are carried out according to the mass ratio of (70-95): (5-20): (5-15) Mixing materials, so that the carbon-oxide electrolyte-coated battery negative electrode material takes into account the performance of charge and discharge capacity, conductivity, and lithium ion conductivity.
本发明所述的碳-氧化物电解质包覆的电池负极材料及其制备方法相较于现有技术具有如下所述的优点以及有益效果：Compared with the prior art, the carbon-oxide electrolyte coated battery negative electrode material and the preparation method thereof have the following advantages and beneficial effects:
本发明所述的碳-氧化物电解质包覆的电池负极材料可以精确地控制碳和氧化物电解质的含量，从而可以实现规模化生产。此外，本发明所述的碳-氧化物电解质包覆的电池负极材料采用碳源有机物和氧化物电解质颗粒煅烧工艺合成得到碳-氧化物电解质包覆的电池负极材料，其中，碳包覆可以有助于改善电池负极材料的导电性(特别是硅碳负极)，氧化物电解质可以有效的改善电池负极材料的锂离子电导率，从而有效的降低阻抗和极化程度，实现改善锂电池电化学性能的目的。The carbon-oxide electrolyte-coated battery negative electrode material of the present invention can accurately control the content of carbon and oxide electrolyte, thereby realizing large-scale production. In addition, the carbon-oxide electrolyte-coated battery negative electrode material of the present invention adopts a carbon source organic matter and oxide electrolyte particle calcination process to synthesize a carbon-oxide electrolyte-coated battery negative electrode material, wherein the carbon coating can have Helps to improve the conductivity of battery anode materials (especially silicon carbon anodes), oxide electrolytes can effectively improve the lithium ion conductivity of battery anode materials, thereby effectively reducing impedance and polarization, and improving the electrochemical performance of lithium batteries the goal of.
另外，所述的电池负极材料由于碳-氧化物电解质含有的杂原子例如N、S、P原子，其不仅可以提高电池负极材料的导电性，还可以为锂离子提供额外的化学位点，从而提高锂电池储锂性能。In addition, due to the heteroatoms such as N, S, and P atoms contained in the carbon-oxide electrolyte, the battery negative electrode material can not only improve the conductivity of the battery negative electrode material, but also provide additional chemical sites for lithium ions, thereby Improve the lithium storage performance of lithium batteries.
此外，本发明所述的制备方法也同样具有上述的优点以及有益效果。In addition, the preparation method of the present invention also has the above-mentioned advantages and beneficial effects.
附图说明Description of the drawings
图1为实施例1的碳-氧化物电解质包覆的电池负极材料的扫描电镜图片；Fig. 1 is a scanning electron microscope picture of the negative electrode material of the battery coated with carbon-oxide electrolyte in Example 1;
图2为实施例2的碳-氧化物电解质包覆的电池负极材料的电化学性能图；2 is a graph of electrochemical performance of the battery negative electrode material coated with carbon-oxide electrolyte in Example 2;
图3为实施例3的碳-氧化物电解质包覆的电池负极材料的电化学性能图。3 is a graph of electrochemical performance of the battery negative electrode material coated with carbon-oxide electrolyte of Example 3. FIG.
具体实施方式detailed description
下面将结合具体的实施例和说明书附图对本发明所述的碳-氧化物电解质包覆的电池负极材料及其制备方法做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。The following will further explain and describe the carbon-oxide electrolyte-coated battery negative electrode material of the present invention and the preparation method thereof in conjunction with specific embodiments and the accompanying drawings. However, the explanation and description are not relevant to the technical solution of the present invention. The composition is improperly qualified.
充放电测试：使用蓝电测试仪通过充放电测试来测试电池的比容量，其中测试电池的电压窗口为0.05～1.5V。分别测试材料在0.1C、0.2C倍率下对应的首次充放电比容量和循环后的比容量(1C＝650mA/g)。库伦效率为充电容量与放电容量的比值。Charging and discharging test: Use the blue electricity tester to test the specific capacity of the battery through the charge and discharge test, and the voltage window of the test battery is 0.05~1.5V. The first charge-discharge specific capacity and the specific capacity after cycling (1C=650mA/g) of the material corresponding to the rate of 0.1C and 0.2C were tested. Coulomb efficiency is the ratio of charge capacity to discharge capacity.
扫描电镜分析(SEM)：将样品添加到乙醇溶液中分散，超声分散5min，用滴管取适量滴到铝箔上，干燥后置于SEM仪器中测试。它通过用聚焦电子束扫描表面来产生样品的图像。电子与样品中的原子相互作用，产生包含样品表面形貌和成分信息的各种信号。采用仪器型号是日本基恩士扫描电镜VE-9800，分辨率：30nm，加速电压0.5-20kV。Scanning electron microscopy analysis (SEM): Add the sample to the ethanol solution for dispersion, ultrasonically disperse for 5 minutes, use a dropper to drop an appropriate amount on the aluminum foil, and place it in the SEM instrument after drying for testing. It produces an image of the sample by scanning the surface with a focused electron beam. Electrons interact with atoms in the sample to generate various signals containing information on the topography and composition of the sample's surface. The instrument model used is Japan Keyence Scanning Electron Microscope VE-9800, resolution: 30nm, acceleration voltage 0.5-20kV.
实施例1Example 1
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的聚环氧乙烯和纳米级别的氧化物电解质LLZO颗粒按照80:10:10的质量份数比例混合，加入5倍质量的氧化锆球(即球料比为5)，以300rpm球磨2h。将得到的粉末放进氮气气氛的管式炉中， 以5℃/min的升温速度加热到700℃，保温2h得到碳-氧化物电解质包覆的电池负极材料。Silicon carbon material, polyethylene oxide as a carbon source organic matter, and nano-level oxide electrolyte LLZO particles are mixed in a mass ratio of 80:10:10, and 5 times the mass of zirconia balls are added (that is, the ball-to-material ratio is 5 ), ball milled at 300rpm for 2h. The obtained powder was put into a tube furnace in a nitrogen atmosphere, heated to 700° C. at a temperature increase rate of 5° C./min, and kept for 2 hours to obtain a carbon-oxide electrolyte-coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在300nm。It should be noted that in this embodiment, the oxide electrolyte particles are 300 nm.
图1为实施例1的碳-氧化物电解质包覆的电池负极材料的扫描电镜图片。FIG. 1 is a scanning electron microscope picture of the battery negative electrode material coated with carbon-oxide electrolyte in Example 1. FIG.
如图1所示，在实施例1的碳-氧化物电解质包覆的电池负极材料中，作为芯部的电池负极材料包覆有碳-氧化物电解质层。As shown in FIG. 1, in the carbon-oxide electrolyte-coated battery negative electrode material of Example 1, the battery negative electrode material as the core is coated with a carbon-oxide electrolyte layer.
实施例2Example 2
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的葡萄糖和纳米级别的氧化物电解质LLZTO颗粒按照80:5:15的质量份数比例混合，加入2倍质量的氧化锆球(即球料比为2)，以350rpm球磨6h。将得到的粉末放进氩气气氛的管式炉中，以10℃/min的升温速度加热到750℃，保温1h得到碳-氧化物电解质包覆的电池负极材料。Silicon-carbon materials, glucose as a carbon source organic matter, and nano-level oxide electrolyte LLZTO particles are mixed in a mass ratio of 80:5:15, and 2 times the mass of zirconia balls (that is, the ball-to-battery ratio is 2) are added to Ball mill at 350rpm for 6h. The obtained powder was put into a tube furnace in an argon atmosphere, heated to 750°C at a temperature increase rate of 10°C/min, and kept for 1 hour to obtain a carbon-oxide electrolyte coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在200nm。图2为实施例2的碳-氧化物电解质包覆的电池负极材料的电化学性能图，方块表示库伦效率，圆形表示放电容量，三角形表示充电容量。It should be noted that in this embodiment, the oxide electrolyte particles are 200 nm. 2 is a graph showing the electrochemical performance of the carbon-oxide electrolyte-coated battery negative electrode material of Example 2. The squares represent the Coulomb efficiency, the circles represent the discharge capacity, and the triangles represent the charge capacity.
如图2所示，实施例2的碳-氧化物电解质包覆的电池负极材料在0.1C(1C＝600mAh g -1)电流密度下可以在循环50次后放电容量仍保持在579mAh g -1。库伦效率均大于99.5％。 As shown in Figure 2, the carbon-oxide electrolyte-coated battery negative electrode material of Example 2 can maintain a discharge capacity of 579mAh g -1 after 50 cycles at a current density of 0.1C (1C=600mAh g -1) . The coulombic efficiencies are all greater than 99.5%.
实施例3Example 3
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的三聚氰胺和纳米级别的氧化物电解质LLZAO颗粒按照75:10:15的质量份数比例混合，加入4倍质量的氧化锆球(即球料比为4)，以500rpm球磨3h。将得到的粉末放进氦气气氛的管式炉中，以2℃/min的升温速度加热到650℃，保温4h得到碳-氧化物电解质包覆的电池负极材料。Silicon-carbon material, melamine as a carbon source organic matter, and nano-level oxide electrolyte LLZAO particles are mixed in a mass ratio of 75:10:15, and 4 times the mass of zirconia balls (that is, the ball-to-battery ratio is 4) is added to Ball mill at 500rpm for 3h. The obtained powder was put into a tube furnace in a helium atmosphere, heated to 650°C at a heating rate of 2°C/min, and kept for 4 hours to obtain a carbon-oxide electrolyte-coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在500nm。It should be noted that in this embodiment, the oxide electrolyte particles are 500 nm.
图3为实施例3的碳-氧化物电解质包覆的电池负极材料的电化学性能图,方块表示库伦效率，圆形表示放电容量，三角形表示充电容量。3 is a graph of electrochemical performance of the battery negative electrode material coated with a carbon-oxide electrolyte of Example 3. The squares represent the Coulomb efficiency, the circles represent the discharge capacity, and the triangles represent the charge capacity.
如图3所示，实施例3的碳-氧化物电解质包覆的电池负极材料在0.2C电流密度下可以在循环80次后放电容量仍保持在548mAh g -1。库伦效率均大于99.5％。 As shown in FIG. 3, the battery negative electrode material coated with carbon-oxide electrolyte of Example 3 can maintain a discharge capacity of 548 mAh g -1 after 80 cycles at a current density of 0.2C. The coulombic efficiencies are all greater than 99.5%.
实施例4Example 4
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的酚醛树脂和纳米级别的氧化物电解质LLZNO颗粒按照75:15:10的质量份数比例混合，加入2倍质量的氧化锆球(即球料比为2)，以250rpm球磨12h。将得到的粉末放进氨气气氛的管式炉中，以2℃/min的升温速度加热到600℃，保温6h得到碳-氧化物电解质包覆的电池负极材料。Silicon carbon material, phenolic resin as a carbon source organic matter, and nano-level oxide electrolyte LLZNO particles are mixed in a ratio of 75:15:10 parts by mass, and 2 times the mass of zirconia balls are added (that is, the ball-to-battery ratio is 2), Ball mill at 250rpm for 12h. The obtained powder was put into a tube furnace in an ammonia gas atmosphere, heated to 600°C at a heating rate of 2°C/min, and kept for 6 hours to obtain a carbon-oxide electrolyte-coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在100nm。It should be noted that in this embodiment, the oxide electrolyte particles are 100 nm.
实施例5Example 5
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的淀粉和纳米级别的氧化物电解质LLZTO颗粒按照90:5:5的质量份数比例混合，加入2倍质量的氧化锆球(即球料比为2)，以450rpm球磨2h。将得到的粉末放进氨气气氛的管式炉中，以15℃/min的升温速度加热到800℃，保温1h得到碳-氧化物电解质包覆的电池负极材料。Silicon carbon material, starch as a carbon source organic matter, and nano-level oxide electrolyte LLZTO particles are mixed in a mass ratio of 90:5:5, and 2 times the mass of zirconia balls (that is, the ball-to-battery ratio is 2) is added to 450rpm ball mill for 2h. The obtained powder was put into a tube furnace in an ammonia atmosphere, heated to 800°C at a temperature increase rate of 15°C/min, and kept for 1 hour to obtain a carbon-oxide electrolyte-coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在50nm。It should be noted that in this embodiment, the oxide electrolyte particles are 50 nm.
实施例6Example 6
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的聚丙烯酸酯和纳米级别的氧化物电解质 LLZNO颗粒按照85:5:10的质量份数比例混合，加入10倍质量的氧化锆球(即球料比为10)，以300rpm球磨2h。将得到的粉末放进氩气气氛的管式炉中，以5℃/min的升温速度加热到650℃，保温3h得到碳-氧化物电解质包覆的电池负极材料。Silicon carbon material, polyacrylate as a carbon source organic matter, and nano-scale oxide electrolyte LLZNO particles are mixed in a mass ratio of 85:5:10, and 10 times the mass of zirconia balls are added (that is, the ball-to-battery ratio is 10) , Ball mill at 300rpm for 2h. The obtained powder was put into a tube furnace in an argon atmosphere, heated to 650°C at a temperature increase rate of 5°C/min, and kept for 3 hours to obtain a carbon-oxide electrolyte coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在250nm。It should be noted that in this embodiment, the oxide electrolyte particles are 250 nm.
实施例7Example 7
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的聚氨酯和纳米级别的氧化物电解质LLZO颗粒按照80:5:15的质量份数比例混合，加入50倍质量的氧化锆球(即球料比为50)，以350rpm球磨2h。将得到的粉末放进氮气气氛的管式炉中，以0.5℃/min的升温速度加热到750℃，保温2h得到碳-氧化物电解质包覆的电池负极材料。Silicon carbon material, polyurethane as a carbon source organic matter, and nano-level oxide electrolyte LLZO particles are mixed in a mass ratio of 80:5:15, and 50 times the mass of zirconia balls (that is, the ball-to-battery ratio is 50) are added to Ball mill at 350rpm for 2h. The obtained powder was put into a tube furnace in a nitrogen atmosphere, heated to 750° C. at a temperature increase rate of 0.5° C./min, and kept for 2 hours to obtain a carbon-oxide electrolyte-coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在100nm。It should be noted that in this embodiment, the oxide electrolyte particles are 100 nm.
实施例8Example 8
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的纤维素和纳米级别的氧化物电解质LLZO颗粒按照85:5:10的质量份数比例混合，加入75倍质量的氧化锆球(即球料比为75)，以600rpm球磨1h。将得到的粉末放进氮气气氛的管式炉中，以5℃/min的升温速度加热到800℃，保温2h得到碳-氧化物电解质包覆的电池负极材料。Silicon carbon material, cellulose as a carbon source organic matter, and nano-level oxide electrolyte LLZO particles are mixed in a mass ratio of 85:5:10, and 75 times the mass of zirconia balls are added (that is, the ball-to-battery ratio is 75), Ball mill at 600rpm for 1h. The obtained powder was put into a tube furnace in a nitrogen atmosphere, heated to 800° C. at a temperature increase rate of 5° C./min, and kept for 2 hours to obtain a carbon-oxide electrolyte coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在150nm。It should be noted that in this embodiment, the oxide electrolyte particles are 150 nm.
实施例9Example 9
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的淀粉和纳米级别的氧化物电解质LLZO颗粒按照85:7.5:7.5的质量份数比例混合，加入100倍质量的氧化锆球(即球料比为100)，以150rpm球磨16h。将得到的粉末放进氮气气氛的管式炉中，以20℃/min的升温速度加热到900℃，保温2h得到碳-氧化物电解质包覆的电池负极材料。Silicon-carbon material, starch as a carbon source organic matter, and nano-level oxide electrolyte LLZO particles are mixed in a mass ratio of 85:7.5:7.5, and 100 times the mass of zirconia balls (that is, the ball-to-battery ratio is 100) are added to 150rpm ball milling for 16h. The obtained powder was put into a tube furnace in a nitrogen atmosphere, heated to 900° C. at a temperature increase rate of 20° C./min, and kept for 2 hours to obtain a carbon-oxide electrolyte-coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在250nm。It should be noted that in this embodiment, the oxide electrolyte particles are 250 nm.
实施例10Example 10
在本实施方式中，碳-氧化物电解质包覆的电池负极材料的制备方法具体如下所述：In this embodiment, the preparation method of the battery negative electrode material coated with carbon-oxide electrolyte is specifically as follows:
硅碳材料、作为碳源有机物的氨基酸和纳米级别的氧化物电解质LLZO颗粒按照90:5:5的质量份数比例混合，加入10倍质量的氧化锆球(即球料比为10)，以100rpm球磨24h。将得到的粉末放进氮气气氛的管式炉中，以10℃/min的升温速度加热到750℃，保温2h得到碳-氧化物电解质包覆的电池负极材料。Silicon-carbon materials, amino acids as carbon source organics, and nano-scale oxide electrolyte LLZO particles are mixed in a mass ratio of 90:5:5, and 10 times the mass of zirconia balls (that is, the ball-to-battery ratio is 10) are added to Ball mill at 100rpm for 24h. The obtained powder was put into a tube furnace in a nitrogen atmosphere, heated to 750° C. at a temperature increase rate of 10° C./min, and kept for 2 hours to obtain a carbon-oxide electrolyte-coated battery negative electrode material.
需要说明的是，在本实施方式中，氧化物电解质颗粒在100nm。It should be noted that in this embodiment, the oxide electrolyte particles are 100 nm.
另外，需要说明的是，上述实施方式中，电池负极材料均采用的是硅碳材料，当然在一些其他的实施方式中，电池负极材料还可以包括硅碳、石墨、软碳、硬碳的至少其中之一。In addition, it should be noted that in the above embodiments, the battery negative electrode materials are all silicon carbon materials. Of course, in some other embodiments, the battery negative electrode materials may also include at least silicon carbon, graphite, soft carbon, and hard carbon. one of them.
此外，对于本发明所述的技术方案中，碳源有机物除上述实施例所示意的以外，其还可以包括聚乙二醇，蔗糖，聚吡咯烷酮，聚四氟乙烯，聚氧化乙烯，双氰胺，环氧树脂中的至少其中之一。In addition, in the technical solution of the present invention, the carbon source organic matter can also include polyethylene glycol, sucrose, polypyrrolidone, polytetrafluoroethylene, polyethylene oxide, and dicyandiamide in addition to what is shown in the above embodiments. , At least one of epoxy resins.
此外，氧化物电解质还可以包括Ba-Sb-Li 7La 3Zr 2O 12，Ge-Li 7La 3Zr 2O 12的至少其中之一。 In addition, the oxide electrolyte may also include at least one of Ba-Sb-Li 7 La 3 Zr 2 O 12 and Ge-Li 7 La 3 Zr 2 O 12.
综上所述可以看出，本发明所述的碳-氧化物电解质包覆的电池负极材料可以精确地控制碳和氧化物电解质的含量，从而可以实现规模化生产。此外，本发明所述的碳-氧化物电解质包覆的电池负极材料采用碳源有机物和氧化物电解质颗粒煅烧工艺合成得到碳-氧化物电解质包覆的电池负极材料，其中，碳包覆可以有助于改善电池负极材料的导电性(特别是硅碳负极)，氧化物电解质可以有效的改善电池负极材料的锂离子电导率，从而有效的降低阻抗和极化程度，实现改善锂电池电化学性能的目的。In summary, it can be seen that the carbon-oxide electrolyte-coated battery negative electrode material of the present invention can accurately control the content of carbon and oxide electrolyte, so that large-scale production can be realized. In addition, the carbon-oxide electrolyte-coated battery negative electrode material of the present invention adopts a carbon source organic matter and oxide electrolyte particle calcination process to synthesize a carbon-oxide electrolyte-coated battery negative electrode material, wherein the carbon coating can have Helping to improve the conductivity of battery anode materials (especially silicon carbon anode), oxide electrolyte can effectively improve the lithium ion conductivity of battery anode materials, thereby effectively reducing impedance and polarization, and improving the electrochemical performance of lithium batteries the goal of.
另外，所述的电池负极材料由于碳-氧化物电解质含有的杂原子例如N、S、P原子，其不仅可以提高电池负极材料的导电性，还可以为锂离子提供额外的化学位点，从而提高锂电池储锂性能。In addition, due to the heteroatoms such as N, S, and P atoms contained in the carbon-oxide electrolyte, the battery negative electrode material can not only improve the conductivity of the battery negative electrode material, but also provide additional chemical sites for lithium ions, thereby Improve the lithium storage performance of lithium batteries.
此外，本发明所述的制备方法也同样具有上述的优点以及有益效果。In addition, the preparation method of the present invention also has the above-mentioned advantages and beneficial effects.
需要说明的是，本发明的保护范围中现有技术部分并不局限于本申请文件所给出的实施例，所有不与本发明的方案相矛盾的现有技术，包括但不局限于在先专利文献、在先公开出版物，在先公开使用等等，都可纳入本发明的保护范围。It should be noted that the prior art part of the protection scope of the present invention is not limited to the embodiments given in this application document, and all prior art that does not contradict the solution of the present invention includes but is not limited to the previous Patent documents, prior publications, prior publications, etc. can all be included in the protection scope of the present invention.
此外，本案中各技术特征的组合方式并不限本案权利要求中所记载的组合方式或是具体实施例所记载的组合方式，本案记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。In addition, the combination of various technical features in this case is not limited to the combination described in the claims of this case or the combination described in the specific embodiments. All technical features described in this case can be freely combined or combined in any way, unless Contradictions arise between each other.
还需要注意的是，以上列举的仅为本发明的具体实施例，显然本发明不限于以上实施例，随之有着许多的类似变化。本领域的技术人员如果从本发明公开的内容直接导出或联想到的所有变形，均应属于本发明的保护范围。It should also be noted that the above-listed are only specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many similar changes follow. If a person skilled in the art directly derives or associates all modifications from the disclosure of the present invention, they shall fall within the protection scope of the present invention.

Claims (11)

  1. 一种碳-氧化物电解质包覆的电池负极材料，其特征在于，其包括：作为芯部的电池负极材料，所述电池负极材料外包覆有碳-氧化物电解质层。A battery negative electrode material coated with a carbon-oxide electrolyte is characterized in that it comprises a battery negative electrode material as a core part, and the battery negative electrode material is coated with a carbon-oxide electrolyte layer.
  2. 如权利要求1所述的碳-氧化物电解质包覆的电池负极材料，其特征在于，所述电池负极材料包括：硅碳、石墨、软碳、硬碳的至少其中之一。The battery negative electrode material coated with carbon-oxide electrolyte according to claim 1, wherein the battery negative electrode material comprises at least one of silicon carbon, graphite, soft carbon, and hard carbon.
  3. 如权利要求1所述的碳-氧化物电解质包覆的电池负极材料，其特征在于，所述碳-氧化物电解质层中的氧化物电解质包括：Li 7La 3Zr 2O 12，0.2Al-Li 7La 3Zr 2O 12，Ba-Sb-Li 7La 3Zr 2O 12，Ge-Li 7La 3Zr 2O 12，Li 6.75La 3Zr 1.75Ta 0.25O 12，Li 6.75La 3Zr 1.75Nb 0.25O 12的至少其中之一。 The carbon-oxide electrolyte coated battery negative electrode material according to claim 1, wherein the oxide electrolyte in the carbon-oxide electrolyte layer comprises: Li 7 La 3 Zr 2 O 12 , 0.2Al- Li 7 La 3 Zr 2 O 12 , Ba-Sb-Li 7 La 3 Zr 2 O 12 , Ge-Li 7 La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 , Li 6.75 La 3 Zr 1.75 At least one of Nb 0.25 O 12.
  4. 一种如权利要求1-3中任意一项所述的碳-氧化物电解质包覆的电池负极材料的制备方法，其特征在于，包括步骤：A method for preparing a carbon-oxide electrolyte-coated battery negative electrode material according to any one of claims 1 to 3, characterized in that it comprises the steps of:
    将电池负极材料、碳源有机物和纳米级别的氧化物电解质颗粒通过球磨进行混料；高温煅烧，以得到所述碳-氧化物电解质包覆的电池负极材料。The battery negative electrode material, carbon source organic matter and nano-level oxide electrolyte particles are mixed through ball milling; high-temperature calcination to obtain the battery negative electrode material coated with the carbon-oxide electrolyte.
  5. 如权利要求4所述的制备方法，其特征在于，所述碳源有机物包括：聚环氧乙烯，聚乙二醇，蔗糖，葡萄糖、聚吡咯烷酮，聚四氟乙烯，聚氧化乙烯，聚丙烯酸酯，聚氨酯，纤维素，淀粉，氨基酸，三聚氰胺，双氰胺，酚醛树脂，环氧树脂中的至少其中之一。The preparation method of claim 4, wherein the carbon source organic matter comprises: polyethylene oxide, polyethylene glycol, sucrose, glucose, polypyrrolidone, polytetrafluoroethylene, polyethylene oxide, polyacrylate , At least one of polyurethane, cellulose, starch, amino acid, melamine, dicyandiamide, phenolic resin, epoxy resin.
  6. 如权利要求4所述的制备方法，其特征在于，所述氧化物电解质颗粒的大小在500nm以下。The preparation method according to claim 4, wherein the size of the oxide electrolyte particles is below 500 nm.
  7. 如权利要求4所述的制备方法，其特征在于，进行球磨的工艺参数满足下述各项：The preparation method according to claim 4, wherein the process parameters for ball milling satisfy the following items:
    球磨速率为100-600rpm；The ball milling speed is 100-600rpm;
    球磨时间为1-24h；Ball milling time is 1-24h;
    球料比为1-100。The ball-to-material ratio is 1-100.
  8. 如权利要求4所述的制备方法，其特征在于，煅烧温度为500-900℃。The preparation method according to claim 4, wherein the calcination temperature is 500-900°C.
  9. 如权利要求4所述的制备方法，其特征在于，煅烧的保护气氛为氮气、氩气、氦气和氨气的至少其中之一。The preparation method according to claim 4, wherein the protective atmosphere for calcination is at least one of nitrogen, argon, helium, and ammonia.
  10. 如权利要求4所述的制备方法，其特征在于，煅烧步骤包括以0.5-20℃/min 的速度升温到煅烧温度，保温0.5-6h。The preparation method according to claim 4, wherein the calcination step comprises heating up to the calcination temperature at a rate of 0.5-20°C/min, and holding the temperature for 0.5-6h.
  11. 如权利要求4所述的制备方法，其特征在于，将电池负极材料、碳源有机物和氧化物电解质颗粒按照(70-95):(5-20):(5-15)的质量份数比例进行混料。The preparation method according to claim 4, characterized in that the battery negative electrode material, carbon source organic matter and oxide electrolyte particles are in a mass ratio of (70-95):(5-20):(5-15) Mixing.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114914422A (en) * 2022-05-19 2022-08-16 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116314834A (en) * 2023-05-25 2023-06-23 四川新能源汽车创新中心有限公司 Composite anode material, preparation method thereof and all-solid-state battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412873A (en) * 2001-10-12 2003-04-23 中国科学院化学研究所 Carbon negative electrode material of lithium ion cell, its preparation method and application
US20120258362A1 (en) * 2011-04-08 2012-10-11 Samsung Electronics Co. Ltd. Electrode active material, method of preparing electrode active material, electrode including electrode active material, and lithium secondary battery including electrode
CN103545497A (en) * 2013-10-18 2014-01-29 中国第一汽车股份有限公司 Lithium ion battery cathode material with two-shell layer structure and preparation method thereof
CN103904304A (en) * 2012-12-28 2014-07-02 惠州比亚迪电池有限公司 Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery
CN104852019A (en) * 2014-02-14 2015-08-19 北京有色金属研究总院 Lithium ion battery silicon metal composite negative electrode material and preparation method thereof
CN108199011A (en) * 2017-11-20 2018-06-22 深圳市斯诺实业发展股份有限公司 A kind of preparation method of lithium titanate anode material
CN108878790A (en) * 2017-05-09 2018-11-23 浙江伏打科技有限公司 A kind of multi-element metal oxide lithium ion battery " [Ma2Oy]1[MjMbkOm]nCarbon " negative electrode material and preparation method thereof
CN109119617A (en) * 2018-08-30 2019-01-01 华为技术有限公司 A kind of silicon substrate composite negative pole material and preparation method thereof and energy storage device
CN110034280A (en) * 2018-03-23 2019-07-19 溧阳天目先导电池材料科技有限公司 A kind of In-situ reaction lithium cell cathode material and its preparation method and application

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8445129B2 (en) * 2005-05-27 2013-05-21 Sony Corporation Cathode active material, method of manufacturing it, cathode, and battery
KR20100073506A (en) * 2008-12-23 2010-07-01 삼성전자주식회사 Negative active material, negative electrode comprising same, method of preparing negative electrode, and lithium battery
CN101847714B (en) * 2010-05-20 2012-10-17 复旦大学 Method for preparing carbon-coated core-shell structure nanometer alloy material of cathode for lithium-ion battery
EP3055269B1 (en) * 2013-10-07 2020-09-09 QuantumScape Corporation Garnet materials for li secondary batteries
CN104091920A (en) * 2014-07-17 2014-10-08 黄冈师范学院 Carbon-coated nano-scale lithium-aluminum alloy negative electrode material and preparation method thereof
CN107579239B (en) * 2017-09-13 2019-11-12 山东大学 A kind of graphene/solid electrolyte compound coating silicon composite cathode and preparation method thereof
CN109818043A (en) * 2017-11-22 2019-05-28 张佳明 A kind of portable lithium battery
CN109616623A (en) * 2018-10-31 2019-04-12 深圳市德方纳米科技股份有限公司 A kind of silicon-based anode material and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412873A (en) * 2001-10-12 2003-04-23 中国科学院化学研究所 Carbon negative electrode material of lithium ion cell, its preparation method and application
US20120258362A1 (en) * 2011-04-08 2012-10-11 Samsung Electronics Co. Ltd. Electrode active material, method of preparing electrode active material, electrode including electrode active material, and lithium secondary battery including electrode
CN103904304A (en) * 2012-12-28 2014-07-02 惠州比亚迪电池有限公司 Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery
CN103545497A (en) * 2013-10-18 2014-01-29 中国第一汽车股份有限公司 Lithium ion battery cathode material with two-shell layer structure and preparation method thereof
CN104852019A (en) * 2014-02-14 2015-08-19 北京有色金属研究总院 Lithium ion battery silicon metal composite negative electrode material and preparation method thereof
CN108878790A (en) * 2017-05-09 2018-11-23 浙江伏打科技有限公司 A kind of multi-element metal oxide lithium ion battery " [Ma2Oy]1[MjMbkOm]nCarbon " negative electrode material and preparation method thereof
CN108199011A (en) * 2017-11-20 2018-06-22 深圳市斯诺实业发展股份有限公司 A kind of preparation method of lithium titanate anode material
CN110034280A (en) * 2018-03-23 2019-07-19 溧阳天目先导电池材料科技有限公司 A kind of In-situ reaction lithium cell cathode material and its preparation method and application
CN109119617A (en) * 2018-08-30 2019-01-01 华为技术有限公司 A kind of silicon substrate composite negative pole material and preparation method thereof and energy storage device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114914422A (en) * 2022-05-19 2022-08-16 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery
CN114914422B (en) * 2022-05-19 2024-03-15 武汉理工大学 Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery

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