CN112290006A - Simple and efficient preparation method of silicon-carbon anode material - Google Patents

Simple and efficient preparation method of silicon-carbon anode material Download PDF

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Publication number
CN112290006A
CN112290006A CN202011325092.2A CN202011325092A CN112290006A CN 112290006 A CN112290006 A CN 112290006A CN 202011325092 A CN202011325092 A CN 202011325092A CN 112290006 A CN112290006 A CN 112290006A
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silicon
carbon
preparation
crushing
graphite
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温广武
张俊亭
王桢
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Shandong Sina New Material Technology Co ltd
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Shandong Sina New Material Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium ion battery materials and preparation thereof, and particularly relates to a simple and efficient preparation method of a silicon-carbon negative electrode material. The method is characterized by comprising the following steps: and uniformly mixing the nano silicon material and the graphite cathode material. The mixed materials are pressed into blocks by a press machine at a certain pressure and then crushed. Briquetting the crushed material with a press at a certain pressure, and then crushing. And repeating the steps for multiple times according to the briquetting and crushing methods to obtain the well-compounded silicon-carbon cathode material. Through the steps of mixing, forging, crushing and the like of the materials, the nano silicon material and the graphite material are uniformly compounded together, the problem of self agglomeration of the nano silicon material in the preparation process of the silicon-carbon cathode material is improved to a certain extent, the layering phenomenon of the material after being prepared into slurry is solved, the obtained silicon-carbon cathode has good electrochemical performance, and the industrial production is easy to realize.

Description

Simple and efficient preparation method of silicon-carbon anode material
Technical Field
The invention belongs to the technical field of lithium ion battery materials and preparation thereof, and particularly relates to a simple and efficient preparation method of a silicon-carbon negative electrode material.
Background
Lithium ion batteries are receiving more and more attention as energy storage devices of portable and new energy power units under the requirements of information, intelligence and digitalization times background. Therefore, the battery has higher requirements on the performance of the battery, and has higher discharge specific energy, excellent cycle performance, good rate performance and the like while meeting the requirements of safety and reliability. Wherein the increase of the energy of the cathode material can reduce the proportion of the cathode material in the whole battery system, thereby increasing the energy density of the whole battery. The performance of the anode material directly affects the performance of the entire battery.
At present, a graphite cathode material is mainly adopted in a commercial lithium ion battery, and the graphite material has great advantages in price and cycle performance, but the theoretical capacity of the battery is relatively low and is 370 mAh/g, and lithium separation can occur during low-temperature charging and rapid charging so as to generate lithium dendrite, thereby affecting the safety performance of the battery. Therefore, a negative electrode material with high capacity, good cycle performance, and safety and reliability is urgently needed to replace the graphite negative electrode material.
The silicon has strong lithium storage capacity, the theoretical capacity is about 4200mAh/g, which is about 10 times of the graphite capacity, and the silicon has rich silicon content and wide source, but because the lithium insertion mechanism of the silicon is different from that of the graphite, lithium atoms can enter the structure of the silicon atoms to form an alloy phase, and the volume of the material expands by more than 300%. The huge volume effect can lead the silicon material to be pulverized and fall off on the current collector, thereby seriously affecting the performance of the battery; on the other hand, silicon is a semiconductor, and poor conductivity is also one of the important reasons that limit its application as a lithium ion negative electrode material.
At present, silicon materials are applied by means of modification of the silicon negative electrode materials, mainly nano modification, surface modification, improvement of matching degree of materials such as electrolyte, binder and the like and silicon, compounding of the materials with graphite to manufacture a silicon-carbon negative electrode and the like. The nano-crystallization is the most important modification mode, and the subsequent preparation of the silicon-carbon anode material by adding nano-silicon into a graphite material becomes the most important mode for commercially improving the anode capacity at present. The silicon-carbon cathode can exert the high capacity characteristic of a silicon material to a certain extent, the graphite can play a role in buffering the expansion of the silicon while exerting the self capacity, and the conductivity of the whole material is improved.
However, the nano silicon material is easy to agglomerate and difficult to disperse, and the nano silicon material are difficult to be uniformly mixed together, so that the application of the nano silicon material in the negative electrode material of the lithium ion battery is hindered to a certain extent.
Disclosure of Invention
Based on the current situation of the silicon-carbon cathode, the invention provides a simple and efficient preparation method of the silicon-carbon cathode, which is characterized by comprising the following steps:
(1) uniformly mixing a nano silicon material and a graphite cathode material;
(2) briquetting the material obtained in the step (1) by a press machine at a certain pressure, and then crushing;
(3) briquetting the material obtained in the step (2) by a press machine at a certain pressure, and then crushing;
(4) and repeating the steps for multiple times according to the briquetting and crushing methods to obtain the well-compounded silicon-carbon cathode material.
Preferably, the nano-silicon negative electrode material is a nano-silicon material with the particle size of 50-200nm, and the graphite negative electrode material is natural graphite or artificial graphite.
Preferably, the proportion of the nano silicon is 5% -20%.
Preferably, when the press is used for pressurizing, the pressure applied to the surface of the material is 0.5-8 MPa.
In a second aspect, the embodiment of the present application claims a silicon carbon negative electrode material prepared by the above preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation method of the silicon-carbon negative electrode material, disclosed by the embodiment of the invention, the nano silicon material and the graphite material are uniformly compounded through the steps of mixing, forging, crushing and the like, so that the problem of self-aggregation of the nano silicon material in the preparation process of the silicon-carbon negative electrode material is improved to a certain extent. The silicon-carbon cathode slurry is uniformly compounded in the early stage of preparation, so that the material is layered after being prepared into the slurry, and the high-capacity performance of the nano silicon material is better exerted;
2. according to the preparation method of the silicon-carbon cathode material, the nano silicon material and the graphite material are uniformly compounded through the steps of mixing, forging, crushing and the like, the preparation method is simple, the obtained silicon-carbon cathode has good electrochemical performance, and industrial production is easy to realize.
Drawings
Fig. 1 is a flow chart of a simple and efficient preparation method of a silicon-carbon negative electrode according to an embodiment of the present invention.
Fig. 2 is a scanning electron microscope photograph of a silicon carbon negative electrode material prepared by the simple and efficient silicon carbon negative electrode preparation method according to the embodiment of the invention.
Fig. 3 is a first-turn charge and discharge performance diagram of the silicon-carbon anode material prepared by the simple and efficient silicon-carbon anode preparation method according to the embodiment of the invention.
Fig. 4 is a cycle performance diagram of a silicon carbon anode material prepared by a simple and efficient silicon carbon anode preparation method according to an example of the present invention.
Fig. 5 is a rate performance diagram of a silicon-carbon anode material prepared by a simple and efficient silicon-carbon anode preparation method according to an example of the present invention.
Detailed Description
Example one
As shown in fig. 1, this example illustrates a simple and efficient method for preparing a silicon carbon anode comprising the steps of:
(1) preparing a silicon-carbon cathode according to the silicon content of 10%, grinding and mixing 0.3g of 150 nm nano silicon material and 2.7g of 2000-mesh artificial graphite powder to uniformly disperse the two materials;
(2) pressing the uniformly dispersed material under the pressure of 2 Mpa to form a briquette, and grinding and crushing the material;
(3) briquetting the crushed material according to the pressure of 2 Mpa, and then grinding and crushing the material;
(4) repeating the above method and parameters for 4 times to obtain the composite silicon-carbon cathode material, as shown in fig. 2.
Mixing the silicon-carbon material with acetylene black and sodium alginate according to the massPreparing slurry according to the ratio of 80:10:10, coating a copper foil to prepare a negative plate, and assembling the negative plate and a metal lithium plate into a button cell for performance test, wherein the electrolyte is 1 mol/L LiPF6The volume ratio of the EC, DMC and EMC mixed solution is 1:1:1, the voltage range is 0.1V-3V, and the nominal specific capacity is 1000 mAh/g. As shown in FIG. 3, the first-loop charging and discharging test curve of the material has the first-loop charging specific capacity of 1601.4 mAh/g, the discharging specific capacity of 1548.96 mAh/g and the efficiency of 96.7 percent. After the material is subjected to 0.1C activation, a 1C cycle performance test is carried out, and the result is shown in FIG. 4, the charging specific capacity of the material after 100 cycles of 1C cycle is 826.8 mAh/g, and the cycle retention rate is 71%. The silicon carbon anode material is subjected to rate capability test, the charging specific capacity after 0.1C circulation for 5 circles is 1568.2 mAh/g, the charging specific capacity after 0.2C circulation for 5 circles is 1059.8 mAh/g, the charging specific capacity after 0.5C circulation for 5 circles is 955.2 mAh/g, the charging specific capacity after 1C circulation for 5 circles is 816.8 mAh/g, and the charging specific capacity after 0.1C circulation for 5 circles is 1405.9 mAh/g, which shows that the silicon carbon anode material prepared by the method has higher specific capacity and good cycle performance and rate capability.
Example two
The embodiment illustrates a simple and efficient preparation method of a silicon-carbon cathode, which comprises the following steps:
(1) preparing a silicon-carbon cathode according to the silicon content of 5%, grinding and mixing 0.15g of 150 nm nano silicon material and 2.85 g of 2000-mesh artificial graphite powder to uniformly disperse the two materials;
(2) then briquetting the uniformly dispersed material according to the pressure of 3 Mpa, and then grinding and crushing the material;
(3) briquetting the crushed material again according to the pressure of 3 Mpa, and then grinding and crushing the material;
(4) repeating the steps for 5 times according to the method and the parameters to obtain the well-compounded silicon-carbon cathode material.
Electrode material preparation, cell assembly and electrochemical performance testing were performed as described in example one. According to a first-circle charging and discharging test curve of the material, the first-circle charging specific capacity is 1408.4 mAh/g, the discharging specific capacity is 1451.8 mAh/g, the efficiency is 97%, the material is subjected to a 1C cycle performance test after being subjected to 0.1C activation, the charging specific capacity of the material is 786.3 mAh/g after being subjected to 1C cycle for 100 circles, and the cycle retention rate is 81%. The silicon carbon anode material is subjected to rate capability test, the charging specific capacity after 0.1C circulation for 5 circles is 1418.2 mAh/g, the charging specific capacity after 0.2C circulation for 5 circles is 989.8 mAh/g, the charging specific capacity after 0.5C circulation for 5 circles is 905.1 mAh/g, the charging specific capacity after 1C circulation for 5 circles is 779.2 mAh/g, and the charging specific capacity after 0.1C circulation for 5 circles is 1389.2 mAh/g, which shows that the silicon carbon anode material prepared by the method has higher specific capacity and good cycle performance and rate capability.
EXAMPLE III
The embodiment illustrates a simple and efficient preparation method of a silicon-carbon cathode, which comprises the following steps:
(1) preparing a silicon-carbon cathode according to the silicon content of 15%, and grinding and mixing 0.45g of 150 nm nano silicon material and 2.55 g of 2000-mesh artificial graphite powder to uniformly disperse the two materials;
(2) then briquetting the uniformly dispersed material according to the pressure of 3 Mpa, and then grinding and crushing the material;
(3) briquetting the crushed material again according to the pressure of 3 Mpa, and then grinding and crushing the material;
(4) repeating the steps for 4 times according to the method and the parameters to obtain the well-compounded silicon-carbon cathode material.
Electrode material preparation, cell assembly and electrochemical performance testing were performed as described in example one. According to a first-circle charging and discharging test curve of the material, the first-circle charging specific capacity is 1912.6 mAh/g, the discharging specific capacity is 2250.1 mAh/g, the efficiency is 85%, the material is subjected to a 1C cycle performance test after being subjected to 0.1C activation, the charging specific capacity of the material is 1000.2 mAh/g after being subjected to 1C cycle for 100 circles, and the cycle retention rate is 75%. The silicon carbon anode material is subjected to rate capability test, the charging specific capacity after 0.1C circulation for 5 circles is 1925.3 mAh/g, the charging specific capacity after 0.2C circulation for 5 circles is 1632.1 mAh/g, the charging specific capacity after 0.5C circulation for 5 circles is 1403.21 mAh/g, the charging specific capacity after 1C circulation for 5 circles is 111.2 mAh/g, and the charging specific capacity after 0.1C circulation for 5 circles is 1799.5 mAh/g, which shows that the silicon carbon anode material prepared by the method has higher specific capacity and good cycle performance and rate capability.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the spirit and scope of the present invention, and various modifications and improvements can be made without departing from the principle of the present invention, which also falls within the scope of the present invention.

Claims (4)

1. A simple and efficient preparation method of a silicon-carbon cathode is characterized by comprising the following steps: (1) uniformly mixing a nano silicon material and a graphite cathode material, (2) briquetting and then crushing the material obtained in the step (1) by a press machine under a certain pressure, (3) briquetting and then crushing the material obtained in the step (2) by the press machine under a certain pressure, and (4) repeating the briquetting and crushing for multiple times according to the method to obtain the compounded silicon-carbon cathode material.
2. The simple and efficient preparation method of the silicon-carbon negative electrode as claimed in claim 1, wherein the adopted nano-silicon negative electrode material is 50-200nm nano-silicon material, and the graphite negative electrode material is natural graphite or artificial graphite.
3. The simple and efficient preparation method of the silicon-carbon cathode as claimed in claim 1, wherein the nano-silicon accounts for 5% -20%.
4. The simple and efficient silicon-carbon cathode preparation method according to claim 1, wherein the pressure applied to the surface of the material when the press is used for pressurizing is 0.5-8 MPa.
CN202011325092.2A 2020-11-23 2020-11-23 Simple and efficient preparation method of silicon-carbon anode material Pending CN112290006A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115172726A (en) * 2022-08-11 2022-10-11 昆明理工大学 Silicon/graphite nano composite material and preparation method and application thereof

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CN107895773A (en) * 2017-12-16 2018-04-10 江西正拓新能源科技股份有限公司 A kind of lithium ion material secondary extracts silicon-carbon compound system
CN109301215A (en) * 2018-09-30 2019-02-01 陕西煤业化工技术研究院有限责任公司 A kind of high capacity silicon-carbon cathode active material and preparation method thereof and its application
CN110690447A (en) * 2019-10-15 2020-01-14 合肥国轩高科动力能源有限公司 Ternary cathode material and preparation method and application thereof
CN111653745A (en) * 2020-05-28 2020-09-11 长沙矿冶研究院有限责任公司 Silicon-carbon negative electrode precursor material, silicon-carbon negative electrode material and preparation method thereof
CN111725504A (en) * 2020-05-26 2020-09-29 深圳市翔丰华科技股份有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102237522A (en) * 2010-05-04 2011-11-09 三星Sdi株式会社 Negative active material and lithium battery
CN107785560A (en) * 2017-11-15 2018-03-09 国联汽车动力电池研究院有限责任公司 A kind of high performance silicon carbon negative pole material and preparation method thereof
CN107895773A (en) * 2017-12-16 2018-04-10 江西正拓新能源科技股份有限公司 A kind of lithium ion material secondary extracts silicon-carbon compound system
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115172726A (en) * 2022-08-11 2022-10-11 昆明理工大学 Silicon/graphite nano composite material and preparation method and application thereof

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Application publication date: 20210129