CN111370693B - Preparation method of silica lithium anode material with high initial efficiency - Google Patents
Preparation method of silica lithium anode material with high initial efficiency Download PDFInfo
- Publication number
- CN111370693B CN111370693B CN202010210661.2A CN202010210661A CN111370693B CN 111370693 B CN111370693 B CN 111370693B CN 202010210661 A CN202010210661 A CN 202010210661A CN 111370693 B CN111370693 B CN 111370693B
- Authority
- CN
- China
- Prior art keywords
- lithium
- silicon
- oxygen
- initial efficiency
- high initial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a silicon-oxygen lithium cathode material with high initial efficiency, which relates to the technical field of batteries, and the preparation method utilizes the characteristic of low melting point of metal lithium and combines the spray drying principle to uniformly mix the silicon-oxygen material and the lithium, and then adopts a wet method or a solid phase method in the post-treatment process to enable the metal lithium to react with oxygen to form lithium silicate, so that the activity of the metal lithium is reduced, and further the initial efficiency of the material is improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a cathode material, and specifically relates to a preparation method of a high-first-efficiency silicon-oxygen lithium cathode material.
Background
It is known that with the continuous development of lithium ion battery technology, the development of high specific energy lithium ion batteries has become an irresistible trend. In order to improve the specific energy of the lithium ion battery, two aspects of the structural design of the lithium ion battery and the development of new materials need to be started, wherein the structural design of the battery mainly reduces the weight of inactive substances such as structural members, copper foils, aluminum foils and the like, and further increases the specific gravity of the active substances and improves the specific energy of the lithium ion battery. In the development of new materials, the positive and negative electrode materials with higher capacity and the positive electrode material with higher voltage are mainly developed, the capacity and the voltage of the battery are improved, and the purpose of improving the energy density of the battery is achieved.
Research shows that the specific energy of the battery can be greatly improved by developing and using the silicon material, because the theoretical capacity of the silicon is more than ten times of that of the existing graphite material. In order to solve the problem that the volume expansion of the crystalline silicon material is large in the charging and discharging processes, the compromise solution is to prepare the silicon monoxide SiOx material. Compared with crystalline silicon materials, the volume expansion of the silicon oxide material in the lithium embedding process is greatly reduced, so that the cycle performance is greatly improved, but the silicon oxide also has the fatal problem of first efficiencyLow in Li content due to the formation of Li in the process of inserting Li into the silicon oxide material 2 O and Li 4 SiO 4 The inactive product, resulting in partial Li deactivation, thus the first efficiency of SiOx materials is typically only around 70%. Because the reversible capacity of the SiOx material is about 1500mAh/g and is much higher than that of the graphite material, under the background that the existing crystalline silicon material preparation technology and material performance do not have great breakthroughs, all large material manufacturers turn to research the SiOx material with better cycle performance, and most silicon cathode materials in the existing market are silicon oxide materials and the like.
Therefore, how to provide a preparation method of a silicon-oxygen-lithium anode material with high first efficiency is a long-term technical demand of the technical personnel in the field.
Disclosure of Invention
In order to overcome the defects in the background technology, the invention provides a preparation method of a silicon-oxygen lithium cathode material with high first-time efficiency.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a silicon-oxygen-lithium anode material with high initial efficiency specifically comprises the following steps:
firstly, mixing a proper amount of micron silicon powder and nano silicon dioxide, and then pressing to form a blocky mixture;
secondly, placing the blocky mixture obtained in the previous step in a heating device for heating, forming a mixed gas of silicon and silicon dioxide when the temperature is heated to 1000-1500 ℃, and condensing at a cooling end of the heating device to obtain a blocky silicon-oxygen precursor;
thirdly, crushing the massive silica precursor obtained in the previous step to obtain a micron-sized or nano-sized material, thereby obtaining a precursor of powder;
fourthly, performing carbon coating on the precursor obtained in the previous step in a liquid phase or gas phase mode;
fifthly, heating the metal lithium at high temperature to obtain a solution of the metal lithium, spraying and pulverizing the liquid metal lithium on the precursor obtained in the previous step under the condition that the carrier gas is inert gas, and spray-drying to obtain a uniform mixture of the metal lithium and the silica material;
and sixthly, carrying out post-treatment on the lithium and silica mixture by adopting a high-temperature or wet method to obtain the silica lithium cathode material with high primary efficiency.
According to the preparation method of the silicon-oxygen-lithium cathode material with high initial efficiency, in the first step, the mixing molar ratio of the micron silicon powder to the nano silicon dioxide is 0.5-2.0.
According to the preparation method of the silicon-oxygen-lithium cathode material with high initial efficiency, in the second step, the heating device comprises an atomizing nozzle, a reaction cavity, a heating source and a pressurizing valve, the heating source is arranged in the reaction cavity, a silicon-silicon dioxide mixture is arranged in the middle of the heating source, the atomizing nozzle is arranged at the upper end of the reaction cavity, and the pressurizing valve is arranged at the lower part of the reaction cavity.
According to the preparation method of the silicon-oxygen-lithium cathode material with high first efficiency, the heating rate of the heating device in the second step is 5-20 ℃/min.
In the third step, the massive silica precursor is crushed in one or a combination of two or more of jaw crushing, air crushing and ball milling.
In the fourth step, the liquid phase takes asphalt as a carbon source, the gas phase mainly takes alkane, alkene and alkyne with low carbon content, and the pyrolysis is carried out at high temperature to obtain the uniform carbon coating layer.
According to the preparation method of the silicon-oxygen lithium cathode material with high initial efficiency, metal lithium is a metal lithium ingot in the fifth step.
According to the preparation method of the silicon-oxygen lithium anode material with high initial efficiency, in the fifth step, metal lithium is heated at high temperature in spraying equipment.
According to the preparation method of the silica lithium cathode material with high initial efficiency, when post-treatment is carried out on a lithium and silica mixture at high temperature in the sixth step, the high-temperature treatment is heating treatment on a cavity of spraying equipment by a solid phase method.
According to the preparation method of the silica lithium cathode material with high initial efficiency, when the wet method is adopted in the sixth step to carry out post-treatment on the lithium and silica mixture, the wet method treatment is wet treatment containing lithium salt, in the treatment process, lithium reacts with oxygen in silica to generate lithium silicate, and active lithium silicate with metal lithium losing strong oxidation can stably exist in air.
By adopting the technical scheme, the invention has the following advantages:
the invention utilizes the characteristic of low melting point of metal lithium, combines the spray drying principle, uniformly mixes the silicon-oxygen material and the lithium, and then adopts a wet method or a solid phase method in the post-treatment process to ensure that the metal lithium reacts with oxygen to form lithium silicate, so as to reduce the activity of the metal lithium and further improve the first efficiency of the material.
Drawings
FIG. 1 is a schematic view of a heating apparatus according to the present invention;
FIG. 2 is a schematic diagram of the first lithium intercalation process of the present invention;
FIG. 3 is a graph showing the results of the cycle performance test of the present invention;
in the figure: 1. a spray nozzle; 2. a reaction chamber; 3. a heating source; 4. a pressurizing valve.
Detailed Description
The present invention will be explained in more detail by the following examples, which are not intended to limit the invention;
the invention relates to a preparation method of a silicon-oxygen-lithium anode material with high first-time efficiency, which specifically comprises the following steps:
firstly, because the melting point of the metal lithium is low, the temperature of the existing spray drying equipment is close to the melting point of the metal lithium, so that the metal lithium can be liquefied, and the metal lithium particles with large specific surface area and uniform size can be obtained by utilizing the spraying process; then mixing a proper amount of micron silicon powder and nano silicon dioxide, and pressing the mixture by a press machine to form a blocky mixture; the method mainly forms uniformly mixed gas in the later gasification process, so that the reaction is more complete. The pure lithium metal ingot is adopted as the lithium metal, and the lithium metal has low activity due to the oxide layer on the surface, so that the lithium metal can be stably stored in a low-humidity environment. The mixing molar ratio of the micron silicon powder to the nano silicon dioxide is 0.5-2.0;
secondly, placing the blocky mixture obtained in the previous step in a heating device for heating, forming a mixed gas of silicon and silicon dioxide when the temperature is heated to 1000-1500 ℃, and condensing at a cooling end of the heating device to obtain a blocky silicon-oxygen precursor; the heating rate of the heating device is 5-20 ℃/min; as shown in fig. 1, the heating device comprises a spray nozzle 1, a reaction chamber 2, a heating source 3 and a pressure valve 4, wherein the heating source 3 is arranged in the reaction chamber 2, a silicon and silicon dioxide mixture is arranged in the middle of the heating source 3, the spray nozzle 1 is arranged at the upper end of the reaction chamber 2, and the pressure valve 4 is arranged at the lower part of the reaction chamber 2;
thirdly, crushing the massive silica precursor obtained in the previous step to obtain a micron-sized or nano-sized material, thereby obtaining a precursor of powder; crushing the massive silica precursor by one or a combination of two or more of jaw crushing, air crushing and ball milling;
and fourthly, the precursor is a silicon-oxygen compound, the electronic conductivity is poor, a layer of conductor, generally carbon or a carbon compound, needs to be coated on the surface of the material, and the precursor obtained in the last step is subjected to carbon coating in a liquid phase or gas phase mode, so that the conductive property of the material is improved, and the silicon-oxygen material with good conductivity is obtained. The liquid phase takes asphalt as a carbon source, the gas phase mainly takes alkane, alkene and alkyne with low carbon content as main components, and the pyrolysis is carried out under the condition of high temperature to obtain a uniform carbon coating layer;
fifthly, heating the metal lithium in a spraying device at a high temperature to obtain a solution of the metal lithium, spraying and pulverizing the liquid metal lithium under the condition that carrier gas is inert gas, spraying the pulverized liquid metal lithium on the precursor obtained in the previous step, and spray-drying to obtain a uniform mixture of the metal lithium and a silica material;
sixthly, the physical mixture of the metal lithium and the silica material prepared in the previous step must be isolated from air, and because the metal lithium has high activity and is easy to oxidize, the mixture of the metal lithium and the silica material is subjected to post-treatment by adopting a high-temperature or wet method, so that the silica lithium cathode material with high first-time efficiency is obtained; when the post-treatment is carried out on the mixture of lithium and silica at high temperature, the high-temperature treatment is to heat the cavity of the spraying equipment by a solid phase method; when the mixture of lithium and silica is subjected to post-treatment by a wet method, the wet treatment is a wet treatment containing lithium salt, in the treatment process, lithium reacts with oxygen in the silica to generate lithium silicate, and the lithium silicate with the activity of losing strong oxidation of metal lithium can stably exist in the air.
When the high-initial-efficiency silica lithium negative electrode material prepared by the method is specifically applied, the prepared material is subjected to electrode preparation, a certain proportion of AM, SP, CMC and SBR is adopted for mixing, a scraper is used for uniformly coating the surface of copper foil, an electrode piece is obtained by vacuum baking, the electrode piece is prepared through cutting and rolling processes, the electrochemical performance of a button cell prepared from the electrode piece and a metal lithium piece is characterized, the electrolyte adopts 1.0Mol/L LiPF6 solution, the solvent composition is EC: EMC =3, and 5% FEC is added into the electrolyte as a negative electrode film forming additive.
The electrochemical performance of the anode material prepared by the invention is characterized as follows: discharging the battery to 0.005V at 0.1C, standing for 5min, and discharging to 0.005V at 0.05C to obtain the first lithium intercalation capacity; the first delithiation capacity was obtained by charging to 1.5V with 0.1C.
The first efficiency = first delithiation capacity/first lithium insertion capacity × 100%
And meanwhile, carrying out cycle performance test on the battery and analyzing the electrochemical performance.
Aiming at the characteristics of the silicon-oxygen-lithium cathode material with high initial efficiency, the silicon-oxygen-lithium compound is synthesized by regulating and controlling experimental conditions and proportion at the front end of production, and the material is subjected to surface modification to prepare the lithium ion battery cathode material with excellent electrochemical performance.
The specific embodiment of the invention is as follows:
firstly, mixing micron silicon and nano silicon dioxide according to a molar ratio of 1; then collecting a massive mixture on a condensation end substrate, wherein the color of the mixture is brown; crushing the blocks in a jaw crushing and ball milling mode, and grading to obtain powder with D50 of 5 to 10um; further, carrying out CVD coating on the obtained silicon-oxygen precursor, wherein an air source is one or a mixture of a plurality of alkanes, alkenes or alkynes with low carbon content, the reaction temperature is 900 ℃, the carbon coating time is 5h, and the surface of the material is coated with a compact carbon layer with the carbon content of 1-20%; further, placing the silica raw material prepared in the previous step into a reaction cavity, liquefying metal lithium at the reaction temperature of 240 ℃, pulverizing the metal lithium by a spray drying method, uniformly mixing the pulverized metal lithium with a silica material, adding a solution containing lithium salt into the cavity after the spray reaction is finished, reacting the metal lithium with silica to obtain silicate, filtering, cleaning and drying the material to obtain a finished product material;
then, preparing an electrode for the obtained material, and evaluating the electrochemical performance and the cycle performance of the material;
FIG. 2 is the first charging and discharging curve of the material, and it can be known from the test data that the first lithium intercalation is 1758mAh/g and the first lithium deintercalation is 1503mAh/g; the efficiency of the material is 85%;
FIG. 3 shows the cycle performance test results of the material, from which it can be seen that the material has excellent electrochemical performance with capacity retention rate of 97% after 20 weeks of cycle;
aiming at the characteristics of the silicon-oxygen lithium cathode material with high first-time efficiency, the lithium-silicon-oxygen compound is synthesized at the front end of production by regulating and controlling experimental conditions and proportion, and the surface of the material is modified to prepare the lithium ion battery cathode material, and the material has excellent electrochemical performance. The invention provides an effective method for preparing the high-performance silicon-oxygen-lithium compound in a large scale at low cost.
The invention mainly adopts a high-temperature spray method to synthesize the high-primary-efficiency lithium ion battery cathode material, adopts a high-temperature spray drying method to spray metal lithium on the surface of a silica mixture, and utilizes a wet method or a solid phase method to synthesize the high-primary-efficiency silica lithium compound. The electrochemical performance test is carried out on the material, the first efficiency of the prepared material is higher than 80%, the gram capacity is larger than 1500mAh/g, and the cycle performance is good.
The present invention is not described in detail in the prior art.
The embodiments chosen for the purpose of disclosure of the invention are presently considered to be suitable, however, it is to be understood that the invention is intended to cover all variations and modifications of the embodiments which fall within the spirit and scope of the invention.
Claims (7)
1. A preparation method of a silica lithium anode material with high initial efficiency is characterized by comprising the following steps: the preparation method specifically comprises the following steps:
firstly, mixing a proper amount of micron silicon powder and nano silicon dioxide, and then pressing to form a blocky mixture;
secondly, placing the block-shaped mixture obtained in the previous step in a heating device for heating, forming a mixed gas of silicon and silicon dioxide when the mixed gas is heated to 1000-1500 ℃, and condensing at the cooling end of the heating device to obtain a block-shaped silica precursor, wherein the heating device comprises a spray nozzle (1), a reaction cavity (2), a heating source (3) and a pressurizing valve (4), the heating source (3) is arranged in the reaction cavity (2), the silicon and silicon dioxide mixture is arranged in the middle of the heating source (3), the spray nozzle (1) is arranged at the upper end of the reaction cavity (2), and the pressurizing valve (4) is arranged at the lower part of the reaction cavity (2);
thirdly, crushing the massive silica precursor obtained in the last step to obtain a micron-scale or nano-scale material, thereby obtaining a precursor of powder;
fourthly, performing carbon coating on the precursor obtained in the previous step in a liquid phase or gas phase mode;
fifthly, placing the silica raw material prepared in the previous step into a reaction cavity, heating metal lithium at high temperature to obtain a solution of metal lithium, spraying and pulverizing liquid metal lithium under the condition that carrier gas is inert gas, spraying the liquid metal lithium on the precursor obtained in the previous step, and performing spray drying to obtain a uniform mixture of the metal lithium and the silica material;
and sixthly, after the spray reaction is finished, adding a solution containing lithium salt into the cavity, reacting the lithium metal with the silicon oxygen material to obtain lithium silicate, and filtering, cleaning and drying the material to obtain a finished product material.
2. The method for preparing the silicon-oxygen-lithium anode material with high initial efficiency as claimed in claim 1, wherein the method comprises the following steps: in the first step, the mixing molar ratio of the micron silicon powder to the nano silicon dioxide is 0.5-2.0.
3. The method for preparing the silicon-oxygen-lithium anode material with high initial efficiency as claimed in claim 1, wherein the method comprises the following steps: the heating rate of the heating device in the second step is 5-20 ℃/min.
4. The method for preparing the silicon-oxygen-lithium anode material with high initial efficiency as claimed in claim 1, wherein the method comprises the following steps: and in the third step, the massive silica precursor is crushed in one or more combined modes of jaw crushing, gas crushing or ball milling.
5. The method for preparing the silicon-oxygen-lithium anode material with high initial efficiency as claimed in claim 1, wherein the method comprises the following steps: in the fourth step, the liquid phase takes asphalt as a carbon source, and the gas-phase carbon source is selected from alkane, alkene and alkyne with low carbon content.
6. The method for preparing the silicon-oxygen-lithium anode material with high initial efficiency as claimed in claim 1, wherein the method comprises the following steps: and in the fifth step, the metal lithium is a metal lithium ingot.
7. The method for preparing the silicon-oxygen-lithium anode material with high initial efficiency as claimed in claim 1, wherein the method comprises the following steps: and in the fifth step, the metallic lithium is heated at high temperature in a spraying device.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010210661.2A CN111370693B (en) | 2020-03-24 | 2020-03-24 | Preparation method of silica lithium anode material with high initial efficiency |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010210661.2A CN111370693B (en) | 2020-03-24 | 2020-03-24 | Preparation method of silica lithium anode material with high initial efficiency |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111370693A CN111370693A (en) | 2020-07-03 |
CN111370693B true CN111370693B (en) | 2022-12-27 |
Family
ID=71212029
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010210661.2A Active CN111370693B (en) | 2020-03-24 | 2020-03-24 | Preparation method of silica lithium anode material with high initial efficiency |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111370693B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113659123B (en) * | 2021-08-16 | 2022-12-02 | 四川金汇能新材料股份有限公司 | Cathode material, preparation method, device and lithium ion battery |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56156677A (en) * | 1980-04-12 | 1981-12-03 | Toshiba Corp | Solid secondary battery |
KR20010111831A (en) * | 2000-06-13 | 2001-12-20 | 김순택 | Lithium-sulfur battery |
CN101304088A (en) * | 2008-06-27 | 2008-11-12 | 三峡大学 | Method for preparing sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material |
KR20150037163A (en) * | 2013-09-30 | 2015-04-08 | 고려대학교 산학협력단 | Method of forming an electrode for a lithium secondary battery |
CN104701509A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and preparation method thereof, and lithium ion battery |
CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
CN106898753A (en) * | 2017-04-17 | 2017-06-27 | 浙江大学 | Silicon coats vertical Graphene/lithium metal composite and its preparation method and application |
CN110311118A (en) * | 2019-07-10 | 2019-10-08 | 洛阳联创锂能科技有限公司 | Disproportionated SiOx material for lithium ion battery and preparation method thereof |
-
2020
- 2020-03-24 CN CN202010210661.2A patent/CN111370693B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56156677A (en) * | 1980-04-12 | 1981-12-03 | Toshiba Corp | Solid secondary battery |
KR20010111831A (en) * | 2000-06-13 | 2001-12-20 | 김순택 | Lithium-sulfur battery |
CN101304088A (en) * | 2008-06-27 | 2008-11-12 | 三峡大学 | Method for preparing sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material |
KR20150037163A (en) * | 2013-09-30 | 2015-04-08 | 고려대학교 산학협력단 | Method of forming an electrode for a lithium secondary battery |
CN104701509A (en) * | 2013-12-06 | 2015-06-10 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and preparation method thereof, and lithium ion battery |
CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
CN106898753A (en) * | 2017-04-17 | 2017-06-27 | 浙江大学 | Silicon coats vertical Graphene/lithium metal composite and its preparation method and application |
CN110311118A (en) * | 2019-07-10 | 2019-10-08 | 洛阳联创锂能科技有限公司 | Disproportionated SiOx material for lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
"Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating";Zheng Liang等;《PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA》;20160315;第113卷;第2862-2867页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111370693A (en) | 2020-07-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2021056981A1 (en) | Preparation method for silicon-based composite negative electrode material for lithium battery | |
WO2021128603A1 (en) | Modified silicon monoxide material for use in negative electrode of lithium-ion battery and preparation method therefor | |
CN110649236B (en) | Porous silicon-carbon composite material and preparation method thereof | |
CN105655564B (en) | SiOx/ C composite negative pole material and its preparation method and application | |
JP7288059B2 (en) | Silicon-oxygen composite negative electrode material, its preparation method and lithium ion battery | |
CN104638240B (en) | Method for preparing lithium ion battery silicon carbon composite anode material and product prepared by method | |
CN112133896B (en) | High-capacity graphite-silicon oxide composite material and preparation method and application thereof | |
CN111710845A (en) | Silica composite negative electrode material, preparation method thereof and lithium ion battery | |
CN111342030A (en) | Multi-element composite high-first-efficiency lithium battery negative electrode material and preparation method thereof | |
CN111048764A (en) | Silicon-carbon composite material and preparation method and application thereof | |
CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
CN108682787B (en) | Lithium ion battery pole piece and preparation method thereof | |
JP2022534241A (en) | Silica particles for electrode material and its production method and application | |
CN108682833B (en) | Preparation method of lithium iron phosphate-based modified cathode material | |
CN113206249B (en) | Lithium battery silicon-oxygen composite anode material with good electrochemical performance and preparation method thereof | |
CN113380998A (en) | Silicon-carbon negative electrode material and preparation method and application thereof | |
CN113506861A (en) | Silicon-based composite negative electrode material of lithium ion battery and preparation method thereof | |
CN108682830B (en) | Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof | |
CN111370693B (en) | Preparation method of silica lithium anode material with high initial efficiency | |
CN110429272B (en) | Silicon-carbon composite negative electrode material with pitaya-like structure and preparation method thereof | |
CN108832183B (en) | Preparation method of lithium ion battery | |
CN111403740A (en) | Preparation method of silica ink composite material | |
CN115818647A (en) | Porous carbon loaded nano silicon material and preparation method and application thereof | |
CN109879286B (en) | Preparation method of lithium battery silicon-carbon negative electrode composite material | |
CN108987689B (en) | Preparation method of silicon-carbon negative electrode material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |