CN116332193A - Method for sintering silicon-oxygen negative electrode material - Google Patents
Method for sintering silicon-oxygen negative electrode material Download PDFInfo
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- CN116332193A CN116332193A CN202310561535.5A CN202310561535A CN116332193A CN 116332193 A CN116332193 A CN 116332193A CN 202310561535 A CN202310561535 A CN 202310561535A CN 116332193 A CN116332193 A CN 116332193A
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- 238000005245 sintering Methods 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 68
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 title claims description 32
- 239000007773 negative electrode material Substances 0.000 title claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000002245 particle Substances 0.000 claims abstract description 88
- 238000000498 ball milling Methods 0.000 claims abstract description 59
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 239000010405 anode material Substances 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 22
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 54
- 229910052744 lithium Inorganic materials 0.000 claims description 54
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- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 15
- 239000002482 conductive additive Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 10
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
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- 239000000463 material Substances 0.000 description 5
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- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/182—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by reduction of a siliceous material, e.g. with a carbonaceous reducing agent and subsequent oxidation of the silicon monoxide formed
-
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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Abstract
The invention provides a method for sintering a silicon oxide anode material, which is used for preparing a silicon oxide anode material and comprises the following steps: ball-milling and mixing silicon powder and silicon dioxide powder to form mixture particles after ball milling; wherein, the mole percent of the silicon powder is as follows: the mole percentages of the silicon dioxide powder are: 40% -50%: 50% -60%; sintering the mixture particles subjected to ball milling and mixing at a high temperature to obtain silicon oxide gas; wherein, the high temperature sintering temperature is: 2000-2500 deg.c; the high-temperature sintering time is as follows: 1-3 min; condensing the silica gas into silica solid particles. The technical scheme provided by the invention solves the problem of overlong preparation time of the silicon oxide in the prior art, thereby greatly shortening the preparation time of the silicon oxide, reducing the energy consumption cost and improving the production efficiency.
Description
Technical Field
The invention relates to the field of lithium battery electrode materials, in particular to a method for sintering a silicon-oxygen anode material.
Background
The traditional preparation method of the silicon-oxygen anode material in the industry adopts lower sintering temperature, so that the reaction speed is slower and the preparation time is long. The method specifically comprises the following steps:
1. the method and the equipment for preparing the high-purity silicon oxide by the frequency induction heating mode specifically comprise the following steps: heating the reactant to 1200-2000 ℃, heating at constant temperature for 3-5h, and cooling at constant temperature for 8-10h; the heating temperature and the raw material proportion can be adjusted to obtain products with different silica ratios; but has a problem of long preparation time.
2. The rotary drum type device collects condensed silicon vapor, mainly solves the problem of uniformity (particle size and mass) of precipitated SiO materials, normally mixes Si and SiO2, heats and gasifies the mixture, conveys the mixture to a rotary silo by inert gas flow, evenly deposits SiO, and heats the mixture to 1000-1500 ℃; there is also a problem in that the process time is too long.
3. Magnesium reduction of silicon oxide by explosion method; the method has the advantages that the first circle coulomb efficiency (magnesium doping) sintering time of the cathode material is improved to 2-12 hours; however, the preparation time is still relatively long, and pure silica materials can not be synthesized;
therefore, developing a preparation process of a silicon-oxygen anode material which can greatly shorten the preparation time of silicon oxide, greatly reduce the energy consumption cost and improve the production efficiency becomes a technical key point to be solved by the technicians in the field.
Disclosure of Invention
The invention provides a method for sintering a silicon oxide anode material, which aims to solve the problem of overlong preparation time of silicon oxide.
According to a first aspect of the present invention, there is provided a method of sintering a silicon oxide negative electrode material for preparing a silicon oxide negative electrode material, comprising:
ball-milling and mixing silicon powder and silicon dioxide powder to form mixture particles after ball milling; wherein, the mole percent of the silicon powder is as follows: the mole percentages of the silicon dioxide powder are: 40% -50%: 50% -60%;
sintering the mixture particles subjected to ball milling and mixing at a high temperature to obtain silicon oxide gas; wherein, the high temperature sintering temperature is: 2000-2500 deg.c; the high-temperature sintering time is as follows: 1-3 min;
condensing the silica gas into silica solid particles.
Optionally, before sintering the mixture particles after ball milling and mixing at high temperature, the method further comprises:
preheating the mixture particles after ball milling and mixing; the preheating temperature is as follows: 1000-1200 ℃; the preheating time is as follows: 1-2 min.
Optionally, after sintering the mixture particles after ball milling and mixing at high temperature, the method further comprises:
heat preservation is carried out at 1000-1200 ℃; the heat preservation time is as follows: 1-2 min.
Optionally, when high-temperature sintering is carried out on the mixture particles after ball milling and mixing, the high-temperature sintering temperature is 2300-2500 ℃; high-temperature sintering time: 2 min-2.5 min.
Optionally, the particle size of the mixture particles after ball milling and mixing is as follows: 2um to 10um.
Optionally, after condensing the silica gas into silica solid particles, the method further comprises:
ball milling and sieving are carried out on the silica solid particles so as to obtain silica ball milling particles with uniform particle size; wherein, the particle size of the silica ball milling particles is as follows: 1um to 2um.
Optionally, sintering the mixture particles after ball milling and mixing by using a joule heating device, wherein the working voltage and the working current of the joule heating device are respectively set as follows: 30A-40A;
300V-400V to provide a high temperature sintering temperature of 2000-2500 ℃.
Optionally, the method for sintering the silicon oxygen anode material comprises the following steps: sintering the mixture particles after ball milling and mixing by adopting a Joule heating device, wherein the working voltage and the working current of the Joule heating device are respectively as follows: 35A to 40A; 350V-400V to provide a high temperature sintering temperature of 2300 ℃ to 2500 ℃.
According to a second aspect of the present invention there is provided a silicon oxygen anode material prepared by the method of sintering a silicon oxygen anode material according to any one of the first aspects of the present invention.
According to a third aspect of the present invention, there is provided a method for preparing a negative electrode sheet of a lithium battery, including the method for sintering a silicon oxygen negative electrode material according to any one of the first aspect of the present invention, the method for preparing a negative electrode sheet of a lithium battery further including:
mixing the silica solid particles, a conductive additive and a binder to prepare a slurry of a negative electrode material; wherein, the mass of the silicon oxide solid particles is as follows: the mass of the conductive additive is as follows:
the mass of the binder is as follows: 90% >: 5%:5%;
wherein the conductive additive comprises: acetylene black and carbon nanotubes; the mass of the acetylene black is as follows:
the mass of the carbon nano tube is as follows: 1:1, a step of;
the binder comprises: sodium carboxymethyl cellulose and styrene butadiene rubber; the mass of the sodium carboxymethyl cellulose is as follows: the styrene-butadiene rubber comprises the following components in percentage by mass: 1:1, a step of;
and coating the slurry of the negative electrode material on a copper foil, and drying to form the lithium battery pole piece.
Optionally, the preparation method of the lithium battery negative electrode piece further comprises the following steps:
cutting the dried lithium battery pole piece into a round pole piece; wherein, the radius of circular pole piece is: 1 to 1.2cm;
vacuumizing and drying the round pole piece in a vacuum drying oven for 8-10 hours; wherein, the stoving temperature is: 100-120 ℃.
Optionally, the conductive additive includes: carbon black.
Optionally, when the slurry of the negative electrode material is coated on the copper foil to be dried, the slurry is dried in a blast drying oven, and the drying temperature is as follows: 45-60 ℃; the drying time is 1-2 hours.
According to a fourth aspect of the invention, a lithium battery negative electrode plate is provided, and the lithium battery negative electrode plate is prepared by the preparation method of the lithium battery negative electrode plate according to the third aspect of the invention.
According to a fifth aspect of the present invention, there is provided a method for preparing a lithium battery, including any one of the method for preparing a lithium battery negative electrode sheet of the fourth aspect of the present invention, the method for preparing a lithium battery further comprising:
providing an anode plate, the lithium battery cathode plate, a diaphragm and electrolyte;
and assembling the positive electrode plate, the lithium battery negative electrode plate, the diaphragm and the electrolyte into a lithium battery.
According to a sixth aspect of the present invention, there is provided a lithium battery prepared by the method for preparing a lithium battery according to the fifth aspect of the present invention.
The invention provides a method for sintering a silicon-oxygen negative electrode material, which comprises the steps of carrying out high-temperature sintering on silicon and silicon dioxide ball-milling mixture particles with a certain mole percentage, and condensing silicon oxide gas into silicon oxide solid particles; wherein, the high temperature sintering temperature is: 2000-2500 deg.c; the high-temperature sintering time is as follows: 1-3 min; therefore, according to the technical scheme provided by the invention, the silicon and silicon dioxide ball-milling mixture particles can be rapidly gasified to generate the silicon oxide gas, so that the preparation time of the silicon oxide can be greatly shortened, the energy consumption cost is reduced, and the production efficiency is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for manufacturing a sintered silicon oxide negative electrode material according to an embodiment of the present invention;
FIG. 2 is a graph of the cycling specific capacity of a lithium battery made from a sintered silicon oxygen negative electrode material according to an embodiment of the present invention;
FIG. 3 is a graph of the cycling specific capacity of a lithium battery made from a sintered silicon oxygen negative electrode material according to another embodiment of the present invention;
FIG. 4 is a graph of the cycling specific capacity of a lithium battery made from a sintered silicon oxygen negative electrode material according to other embodiments of the present invention;
FIG. 5 is a schematic view of a Joule heating apparatus according to an embodiment of the present invention;
reference numerals illustrate:
1-a graphite tube;
2-a conductive mold clip;
3-power supply;
4-voltmeter;
5-ammeter;
6-resistance.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The terms "first," "second," "third," "fourth" and the like in the description and in the claims and in the above drawings, if any, are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The traditional preparation method of the silicon-oxygen anode material in the industry adopts lower sintering temperature, so that the reaction speed is slower, the preparation time is long (generally, the temperature is raised for 4-5 hours, the temperature is kept for 3-5 hours, and the cooling is carried out for 8-10 hours); and also the following limitations: b. the requirement on the vacuum degree of the equipment is high (less than or equal to 15 Pa); c. the synthesis cost is high: 50% of the current material synthesis costs are energy consumption costs.
In view of this, the inventors of the present application made a series of studies and experiments on a method of sintering a silicon oxide anode material by preparing the silicon oxide anode material using an ultrafast sintering apparatus, found that: the mixed powder of SiO2 and Si is gasified rapidly, so that the preparation time of the silicon oxide can be greatly shortened, the energy consumption cost is reduced, and the production efficiency is improved.
The technical scheme of the invention is described in detail below by specific examples. The following embodiments may be combined with each other, and some embodiments may not be repeated for the same or similar concepts or processes.
Referring to fig. 1 to 5, according to an embodiment of the present invention, there is provided a method for sintering a silicon oxide anode material, a process flow chart of the method for preparing a silicon oxide anode material, the method for sintering a silicon oxide anode material is shown in fig. 1, the method includes:
s11: ball-milling and mixing silicon powder and silicon dioxide powder to form mixture particles after ball milling; wherein, the mole percent of the silicon powder is as follows: the mole percentages of the silicon dioxide powder are: 40% -50%: 50% -60%;
s12: sintering the mixture particles subjected to ball milling and mixing at a high temperature to obtain silicon oxide gas; wherein, the high temperature sintering temperature is: 2000-2500 deg.c; the high-temperature sintering time is as follows: 1-3 min;
s13: condensing the silica gas into silica solid particles.
In step S11, silicon powder: 40-50% (mole percent) of silicon dioxide powder: ball-milling and mixing 50-60% (mole percent) to form ball-milled mixture particles; the specific reference is as follows: in the mixture particles after ball milling, the silicon powder accounts for the following proportion: 40-50% (mole percent), the silicon dioxide powder accounts for: 50-60% (mole percent).
The invention provides a method for sintering a silicon-oxygen negative electrode material, which comprises the steps of carrying out high-temperature sintering on silicon and silicon dioxide ball-milling mixture particles with a certain mole percentage, and condensing silicon oxide gas into silicon oxide solid particles; wherein, the high temperature sintering temperature is: 2000-2500 deg.c; the high-temperature sintering time is as follows: 1-3 min; therefore, according to the technical scheme provided by the invention, the silicon and silicon dioxide ball-milling mixture particles can be rapidly gasified to generate the silicon oxide gas, so that the preparation time of the silicon oxide can be greatly shortened, the energy consumption cost is greatly reduced, and the production efficiency is improved.
Further, since the physical properties of Si and SiO2 are changed by the rapid heating mode, the gasification temperature of Si and SiO2 is reduced, thereby being more beneficial to the preparation of SiO.
In theory, the smaller the particle size of the mixture particles after ball milling and mixing is, the better the effect is, but the energy consumption is high, which is not beneficial to mass production; the too large particle size of the mixture particles after ball milling mixing may cause insufficient mixing and may also be affected during gasification at high temperature sintering. Thus, in a preferred embodiment, the mixture particles after ball milling are of the particle size: 2um to 10um.
In one embodiment, in step S12, before sintering the mixture particles after ball milling and mixing at high temperature, the method further includes:
preheating the mixture particles after ball milling and mixing;
the preheating function of the mixture particles after ball milling and mixing is as follows: so that the sintering is more sufficient. Too short a preheating time may result in uneven gasification; thereby affecting the quality of the finally produced silica;
thus, in a preferred embodiment, the preheating temperature is: 1000-1200 ℃; the preheating time is as follows: 1-2 min.
In other embodiments, the implementation manners of the preheating temperature and the preheating time may be other implementations, which are not limited to the present invention.
In one embodiment, in step S12, after performing high-temperature sintering on the mixture particles after ball milling and mixing, the method further includes:
heat preservation is carried out at 1000-1200 ℃;
wherein, the effect of carrying out heat preservation to the mixture particles after high-temperature sintering is: the uniform condensation of steam is facilitated, and the insufficient condensation of the steam can be caused due to the short condensation time, so that the yield of solid mixture particles is reduced;
in a preferred embodiment, the incubation time is: 1-2 min.
In other embodiments, the implementation manner of the heat preservation time may be other implementations, which is not limited to the present invention.
In one embodiment, in step S12, sintering the mixture particles after ball milling and mixing by using a joule heating device, where the working voltage and the working current of the joule heating device are set as follows: 30A-40A; 300V-400V to provide a high temperature sintering temperature of 2000-2500 ℃.
As shown in fig. 5, which is a schematic view of the joule heating apparatus, the joule heating apparatus includes: graphite tube 1, ammeter 5, voltmeter 4, resistor 6 and power supply 3; wherein, the power supply 3, the resistor 6, the ammeter 5 and the graphite tube 1 are sequentially connected in series; the voltmeter 4 is connected in parallel with two ends of the graphite tube 1; the graphite tube 1 is connected with the two ends of the voltmeter 4 through the conductive die clamp 2.
When the mixture particles after ball milling are sintered by using a Joule heating device, the specific operation steps are described as follows:
1. loading the mixture particles after ball milling and mixing into a graphite tube 1; wherein a vacuum environment is set in the graphite tube 1 (the vacuum degree is set to be less than 500 Pa);
compared with the prior art that the vacuum degree of equipment is required to be less than or equal to 15Pa, the technical scheme provided by the patent has lower requirement on the vacuum degree;
2. connecting a power supply 3, setting output voltage and current to control temperature, and starting an external circuit; the voltage and the current can be regulated in the middle to control the temperature;
and 3, closing the device when the time is reached, namely, the temperature is reduced (consistent with the temperature rising rate), and taking out the powder.
Similar joule devices can be seen in: the third page of the high temperature ultrafast material preparation device HTS and FJH introduction V2.1 and the product atlas-2023.02 of the in situ technology Co., ltd.
The voltage output controllable by the Joule heating device adopted by the invention is as follows: the current output is 0-40V: 0-500A; the Joule heating device adopted by the invention has high safety, and is suitable for high-temperature sintering at the temperature of more than 2000 ℃.
In a preferred embodiment, in step S12, when the mixture particles after ball milling and mixing are sintered at a high temperature, the high temperature sintering temperature is 2300 ℃ to 2500 ℃; high-temperature sintering time: 2 min-2.5 min.
Correspondingly, in one embodiment, the mixture particles after ball milling and mixing are sintered by a joule heating device, and the working voltage and the working current of the joule heating device are set as follows: 35A to 40A; 350V-400V to provide a high temperature sintering temperature of 2300 ℃ to 2500 ℃.
The present invention will be analyzed experimentally in providing a high temperature sintering temperature of: the sintering time at the high temperature is 2300-2500 ℃, and the sintering time at the high temperature is as follows: 2 min-2.5 min, the product performance of the silicon-oxygen anode material in some specific embodiments; a constant-current charge and discharge mode test is carried out by using a charge and discharge instrument; wherein, the discharge cut-off voltage is 0.05V, the charge cut-off voltage is 1V, the first round of charge and discharge test is performed under C/20 current density, and the fourth round and subsequent discharge tests are performed under C/2 current density.
Specific example 1:
high-temperature sintering temperature is 2500 ℃, and sintering time is 2 minutes;
referring to fig. 2, fig. 2 shows a graph of the cycle specific capacity of a lithium battery including the silicon oxygen anode material prepared in example 1.
As can be seen from FIG. 2, the activation of C/20 was performed three times before 0.05V-1V, and 0.5C long cycles were performed at 0.05V-1V; wherein after 300 circles of circulation, the specific capacity is 958mAh/g, and the corresponding specific capacity retention rate is as follows: 79.4%. From this, it is seen that in example 1, a silicon oxide anode material having relatively good performance was produced by sintering at a high temperature for a relatively long time.
Specific example 2:
high-temperature sintering temperature is 2000 ℃, sintering time is 2 minutes;
referring to fig. 3, fig. 3 shows a graph of the cycle specific capacity of a lithium battery including the silicon oxygen anode material prepared in example 2.
As can be seen from fig. 3, the specific capacity after 300 circles is 556mAh/g, the corresponding specific capacity retention rate is 45.9%, and the cycle performance is obviously reduced when the sintering temperature is reduced; this is due to insufficient sintering, where there is some residual of insufficiently sintered SiO2, and where this part itself is an electrically inert substance, which affects the conductive network in the whole electrode and thus the electrochemical performance.
Specific example 3:
high-temperature sintering temperature is 2500 ℃, and sintering time is 1 minute;
referring to fig. 4, fig. 4 shows a graph of the cycle specific capacity of a lithium battery including the silicon oxygen anode material prepared in example 3.
As can be seen from fig. 4, at 0.5C, the initial capacity is 1055mAh/g, the subsequent cycle has obvious climbing process, the residual capacity after 300 cycles has 938mAh/g, and the corresponding capacity retention rate is 74.3%; it can be seen that as the sintering time decreases, a significant decrease in rate capability can be seen.
After the mixture particles after ball milling and mixing are sintered at high temperature to obtain silicon oxide gas, in step S13, the condensation mode adopted when condensing the silicon oxide gas into silicon oxide solid particles is as follows: natural condensation; the condensing time is as follows: 1 min-2 min. The condensing time described herein is a proper natural condensing time, and the condensing time is not limited herein, and a specific condensing time may be selected as the case may be.
In one embodiment, step S13, after condensing the silica gas into silica solid particles, further includes:
ball milling and sieving are carried out on the silica solid particles so as to obtain silica ball milling particles with uniform particle size; wherein, the particle size of the silica ball milling particles is as follows: 1um to 2um.
Wherein, the too large particle size of the silica ball milling particles can lead to the reduction of the overall conductivity, thereby reducing the cycle performance of the battery. The particle size of the silicon oxide ball-milling particles is too small, and the energy consumption is large, and when the silicon oxide ball-milling particles are ball-milled into nano-scale particles, a high-energy ball-milling mode is needed, and the energy consumption is large.
According to an embodiment of the present invention, there is also provided a silicon-oxygen anode material prepared by the method for sintering a silicon-oxygen anode material according to any one of the preceding embodiments of the present invention.
Secondly, according to an embodiment of the present invention, there is further provided a method for preparing a negative electrode sheet of a lithium battery, including the method for sintering a silicon oxygen negative electrode material according to any one of the foregoing embodiments of the present invention, the method for preparing a negative electrode sheet of a lithium battery further includes:
mixing the silica solid particles, a conductive additive and a binder to prepare a slurry of a negative electrode material; wherein, the mass of the silicon oxide solid particles is as follows: the mass of the conductive additive is as follows: the mass of the binder is as follows: 90% >: 5%:5%;
wherein the conductive additive comprises: acetylene black and carbon nanotubes; the mass of the acetylene black is as follows: the mass of the carbon nano tube is as follows: 1:1, a step of;
the binder comprises: sodium carboxymethyl cellulose and styrene butadiene rubber; the mass of the sodium carboxymethyl cellulose is as follows: the styrene-butadiene rubber comprises the following components in percentage by mass: 1:1.
and coating the slurry of the negative electrode material on a copper foil, and drying to form the lithium battery pole piece.
In one embodiment, the preparation method of the lithium battery negative electrode piece further comprises the following steps:
cutting the dried lithium battery pole piece into a round pole piece; wherein, the radius of circular pole piece is: 1 to 1.2cm;
vacuumizing and drying the round pole piece in a vacuum drying oven for 8-10 hours; wherein, the stoving temperature is: 100-120 ℃.
In one embodiment, the conductive additive includes: carbon black.
In one embodiment, when the slurry of the negative electrode material is coated on the copper foil and dried, the slurry is dried in a blast drying oven at the following drying temperature: 45-60 ℃; the drying time is 1-2 hours.
In addition, according to an embodiment of the present invention, there is also provided a lithium battery negative electrode sheet, which is prepared by using the preparation method of the lithium battery negative electrode sheet according to the foregoing embodiment of the present invention.
Again, according to an embodiment of the present invention, there is further provided a method for preparing a lithium battery, including the method for preparing a lithium battery negative electrode sheet according to any one of the foregoing embodiments of the present invention, the method for preparing a lithium battery further includes:
providing an anode plate, the lithium battery cathode plate, a diaphragm and electrolyte;
and assembling the positive electrode plate, the lithium battery negative electrode plate, the diaphragm and the electrolyte into a lithium battery.
Finally, according to an embodiment of the present invention, there is also provided a lithium battery manufactured by using the method for manufacturing a lithium battery according to the foregoing embodiment of the present invention.
The following conditions for sintering provided by the invention are: the method for sintering the silicon-oxygen anode material is specifically described by taking a high-temperature sintering temperature of 2500 ℃ and a high-temperature sintering time of 2 minutes as an example:
1. the silicon powder and the silicon dioxide powder after ball milling and mixing are filled into a graphite tube 1 (specifically, the graphite tube 1 can be a graphite boat), the device is pumped to a low vacuum state (500 pa), the output voltage is set to 40V, the current is set to 400A, the temperature is cut off to 2500 ℃, and the heat is preserved for 2 minutes.
When the switch is turned on, electric joule heating is started, the temperature of the graphite tube 1 is rapidly increased to 2500 ℃, raw materials start to react and sublimate, and collision heat exchange is carried out in the process, so that a uniform SiO product is formed.
2. Turning off the power supply 3, and at the moment, no voltage or current exists, rapidly cooling the graphite tube 1 to room temperature, waiting for 5 minutes, and condensing the high-purity silicon oxide SiO finished product into solid;
3. taking out the materials, ball milling again, and sieving to obtain SiO particles (-2 um) with uniform particle size.
4. The silicon dioxide with uniform particle size obtained above is used as a cathode active material, and is mixed with carbon black as a conductive additive, sodium carboxymethyl cellulose as a binder and styrene-butadiene rubber (the mass ratio is 1:1) according to the mass ratio of 95%:2%:3% is weighed, and the mixture is put into a refiner at room temperature for slurry preparation. And uniformly coating the prepared slurry on the copper foil. Drying in a blast drying oven at 60deg.C for 2 hr, cutting into 8×8mm pole pieces, and vacuum drying in a vacuum drying oven at 100deg.C for 10 hr. Transferring the dried pole piece into a glove box for standby use to assemble a battery; wherein, the assembly of the battery is carried out in a glove box containing high-purity Ar atmosphere.
5. LiPF with metallic lithium as counter electrode, 1M 6 The dispersion in Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) (volume ratio v: v=45:45:10) was used as an electrolyte to assemble a battery.
6. The constant current charge and discharge mode test was performed using a charge and discharge meter, with a discharge cut-off voltage of 0.05V and a charge cut-off voltage of 1V, with a first week of charge and discharge test at C/20 current density, and a fourth week and subsequent discharge tests at C/2 current density.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (16)
1. A method of sintering a silicon oxide negative electrode material, comprising:
ball-milling and mixing silicon powder and silicon dioxide powder to form mixture particles after ball milling; wherein, the mole percent of the silicon powder is as follows: the mole percentages of the silicon dioxide powder are: 40% -50%: 50% -60%;
sintering the mixture particles subjected to ball milling and mixing at a high temperature to obtain silicon oxide gas; wherein, the high temperature sintering temperature is: 2000-2500 deg.c; the high-temperature sintering time is as follows: 1-3 min;
condensing the silica gas into silica solid particles.
2. The method of sintering a silicon oxygen anode material according to claim 1, further comprising, before high temperature sintering the mixture particles after ball milling and mixing:
preheating the mixture particles after ball milling and mixing; the preheating temperature is as follows: 1000-1200 ℃; the preheating time is as follows: 1-2 min.
3. The method of sintering a silicon oxygen anode material according to claim 1, further comprising, after high temperature sintering the mixture particles after ball milling and mixing:
heat preservation is carried out at 1000-1200 ℃; the heat preservation time is as follows: 1-2 min.
4. A method of sintering a silicon oxygen anode material according to any one of claims 2 or 3, wherein when the mixture particles after ball milling and mixing are subjected to high temperature sintering, the high temperature sintering temperature is 2300 ℃ to 2500 ℃; high-temperature sintering time: 2 min-2.5 min.
5. The method of sintering a silicon oxygen anode material according to claim 4, wherein the particle size of the mixture particles after ball milling mixing is: 2um to 10um.
6. The method of sintering a silicon oxygen anode material of claim 5, further comprising, after condensing the silicon oxide gas into silicon oxide solid particles:
ball milling and sieving are carried out on the silica solid particles so as to obtain silica ball milling particles with uniform particle size; wherein, the particle size of the silica ball milling particles is as follows: 1um to 2um.
7. The method for sintering a silicon-oxygen anode material according to claim 6, wherein the mixture particles after ball milling and mixing are sintered by a joule heating device, and the working voltage and the working current of the joule heating device are set as follows: 30A-40A; 300V-400V to provide a high temperature sintering temperature of 2000-2500 ℃.
8. The method of sintering a silicon oxygen anode material of claim 7, comprising: sintering the mixture particles after ball milling and mixing by adopting a Joule heating device, wherein the working voltage and the working current of the Joule heating device are respectively as follows: 35A to 40A; 350V-400V to provide a high temperature sintering temperature of 2300 ℃ to 2500 ℃.
9. A silicon-oxygen negative electrode material characterized by being prepared by the method for sintering a silicon-oxygen negative electrode material according to any one of claims 1 to 8.
10. A method for preparing a negative electrode plate of a lithium battery, which is characterized by comprising the method for sintering a silicon oxide negative electrode material according to any one of claims 1 to 8, and further comprising the steps of:
mixing the silica solid particles, a conductive additive and a binder to prepare a slurry of a negative electrode material; wherein, the mass of the silicon oxide solid particles is as follows: the mass of the conductive additive is as follows: the mass of the binder is as follows: 90% >: 5%:5%;
wherein the conductive additive comprises: acetylene black and carbon nanotubes; the mass of the acetylene black is as follows: the mass of the carbon nano tube is as follows: 1:1, a step of;
the binder comprises: sodium carboxymethyl cellulose and styrene butadiene rubber; the mass of the sodium carboxymethyl cellulose is as follows: the styrene-butadiene rubber comprises the following components in percentage by mass: 1:1, a step of;
and coating the slurry of the negative electrode material on a copper foil, and drying to form the lithium battery pole piece.
11. The method for preparing a negative electrode tab of a lithium battery according to claim 10, further comprising:
cutting the dried lithium battery pole piece into a round pole piece; wherein, the radius of circular pole piece is: 1 to 1.2cm;
vacuumizing and drying the round pole piece in a vacuum drying oven for 8-10 hours; wherein, the stoving temperature is: 100-120 ℃.
12. The method for preparing a negative electrode tab for a lithium battery according to claim 11, wherein the conductive additive comprises: carbon black.
13. The method for preparing a negative electrode sheet of a lithium battery according to claim 12, wherein when the slurry of the negative electrode material is coated on a copper foil and dried, the drying is performed in a blast drying oven at the following drying temperature: 45-60 ℃; the drying time is 1-2 hours.
14. A lithium battery negative electrode plate, characterized in that the lithium battery negative electrode plate is prepared by the preparation method of the lithium battery negative electrode plate according to claims 10-13.
15. A method for preparing a lithium battery, comprising the method for preparing a lithium battery negative electrode sheet according to any one of claims 10 to 13, the method further comprising:
providing an anode plate, the lithium battery cathode plate, a diaphragm and electrolyte;
and assembling the positive electrode plate, the lithium battery negative electrode plate, the diaphragm and the electrolyte into a lithium battery.
16. A lithium battery prepared by the method of claim 15.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109589A (en) * | 2001-09-28 | 2003-04-11 | Mitsubishi Materials Corp | Lithium battery negative electrode activator, manufacturing method of the same, and negative electrode using the same |
| CN105793194A (en) * | 2013-11-28 | 2016-07-20 | 魁北克电力公司 | Method for preparing SiOx having a nanometric filament structure, and use thereof as a lithium-ion battery anode material |
| CN106744985A (en) * | 2016-12-30 | 2017-05-31 | 天津惠利科技股份有限公司 | Silicon monoxide nano material and preparation method thereof |
| CN108946744A (en) * | 2018-07-23 | 2018-12-07 | 江苏载驰科技股份有限公司 | A kind of lithium ion battery preparation method for aoxidizing sub- silicium cathode material |
| WO2021128603A1 (en) * | 2019-12-27 | 2021-07-01 | 江西壹金新能源科技有限公司 | Modified silicon monoxide material for use in negative electrode of lithium-ion battery and preparation method therefor |
| CN113258159A (en) * | 2021-05-06 | 2021-08-13 | 哈尔滨工程大学 | Device and method for regenerating lithium ion battery electrode material |
| CN113620301A (en) * | 2017-05-05 | 2021-11-09 | 储晞 | Method and device for producing silicon monoxide |
| CN114388770A (en) * | 2022-01-24 | 2022-04-22 | 浙江锂宸新材料科技有限公司 | High-capacity high-first-efficiency silica anode material and preparation method thereof |
| CN114649503A (en) * | 2020-12-18 | 2022-06-21 | 懋青恺有限公司 | Lithium battery silicon-carbon negative plate and preparation method thereof |
-
2023
- 2023-05-18 CN CN202310561535.5A patent/CN116332193A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109589A (en) * | 2001-09-28 | 2003-04-11 | Mitsubishi Materials Corp | Lithium battery negative electrode activator, manufacturing method of the same, and negative electrode using the same |
| CN105793194A (en) * | 2013-11-28 | 2016-07-20 | 魁北克电力公司 | Method for preparing SiOx having a nanometric filament structure, and use thereof as a lithium-ion battery anode material |
| CN106744985A (en) * | 2016-12-30 | 2017-05-31 | 天津惠利科技股份有限公司 | Silicon monoxide nano material and preparation method thereof |
| CN113620301A (en) * | 2017-05-05 | 2021-11-09 | 储晞 | Method and device for producing silicon monoxide |
| CN108946744A (en) * | 2018-07-23 | 2018-12-07 | 江苏载驰科技股份有限公司 | A kind of lithium ion battery preparation method for aoxidizing sub- silicium cathode material |
| WO2021128603A1 (en) * | 2019-12-27 | 2021-07-01 | 江西壹金新能源科技有限公司 | Modified silicon monoxide material for use in negative electrode of lithium-ion battery and preparation method therefor |
| CN114649503A (en) * | 2020-12-18 | 2022-06-21 | 懋青恺有限公司 | Lithium battery silicon-carbon negative plate and preparation method thereof |
| CN113258159A (en) * | 2021-05-06 | 2021-08-13 | 哈尔滨工程大学 | Device and method for regenerating lithium ion battery electrode material |
| CN114388770A (en) * | 2022-01-24 | 2022-04-22 | 浙江锂宸新材料科技有限公司 | High-capacity high-first-efficiency silica anode material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SONGSASEN, A等: ""Microfibrous solids derived from SiO and from other main group oxide vapours"", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 10, no. 02, 1 February 2000 (2000-02-01), pages 347 - 351 * |
| 陈新亮: "" 热等离子法制备纳米氧化亚硅的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 (月刊)》, no. 04, 15 April 2021 (2021-04-15), pages 015 - 98 * |
| 陈新亮;万小涵;马文会;魏奎先;李绍元;: "功率对热等离子法制备纳米SiO的影响及其锂电池性能测试", 有色金属工程, no. 07, 25 July 2020 (2020-07-25) * |
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