CN110880592A - Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof - Google Patents

Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof Download PDF

Info

Publication number
CN110880592A
CN110880592A CN201911221776.5A CN201911221776A CN110880592A CN 110880592 A CN110880592 A CN 110880592A CN 201911221776 A CN201911221776 A CN 201911221776A CN 110880592 A CN110880592 A CN 110880592A
Authority
CN
China
Prior art keywords
gas
carbon
sccm
mixed gas
silicon
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.)
Pending
Application number
CN201911221776.5A
Other languages
Chinese (zh)
Inventor
亓钧雷
王鹏程
钟正祥
闫耀天
曹健
冯吉才
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201911221776.5A priority Critical patent/CN110880592A/en
Publication of CN110880592A publication Critical patent/CN110880592A/en
Pending legal-status Critical Current

Links

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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 discloses a carbon-carbon nanotube-silicon nanoparticle and a preparation method and application thereof, and belongs to the field of preparation of energy storage materials. The invention mainly solves the problems of large volume change, too low intrinsic electronic conductivity and poor interface binding force of the traditional silicon cathode material in the charging and discharging processes. The method of the invention carries out chemical vapor deposition on silicon nano particles in the mixed atmosphere of argon and hydrogen, then carries out plasma vapor deposition on a carbon layer, and then grows the carbon nano tube by a floating catalyst method. The in-situ preparation of the invention realizes the tight combination between the carbon nano tube and the carbon layer, buffers the volume expansion effect of silicon, and the carbon nano tubes which are mutually crosslinked can form a conductive network, thereby being beneficial to the quick conduction of the composite material. The carbon-carbon nanotube-silicon nanoparticle composite electrode material prepared by the invention has the advantages of quick preparation, good dispersibility, controllable size and good electrochemical performance, and is a lithium battery cathode material with wide application prospect.

Description

Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of energy storage materials; in particular to a carbon-carbon nano tube-silicon nano particle and a preparation method and application thereof.
Background
With the development of economy and society at present, the development of clean, safe and renewable novel energy becomes the focus of research at present, and lithium batteries are widely applied in more and more fields as an energy storage device capable of providing portable energy. The lithium battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm and electrolyte. The traditional lithium battery negative electrode material is mainly graphite, but the theoretical specific capacity of the graphite is lower, so that the further improvement of the overall energy density of the lithium battery is limited, and therefore, a high-performance novel lithium battery negative electrode material needs to be developed.
Among the many lithium battery negative electrode materials, the silicon negative electrode has its high theoretical specific mass capacity (4200mAh g)-1) Specific volume capacity (9786mAh cm)-3) The silicon cathode has the advantages of low average discharge potential (as low as 0.4V), rich resources, environmental friendliness, no toxicity and the like, so that the silicon cathode becomes the next-generation lithium battery cathode material with the most potential. However, the current silicon negative electrode still has the problems of poor cycle performance, coulombic efficiency and rate capability, and further the practical application of the silicon negative electrode is severely limited. Considering that the energy storage mechanism of the silicon negative electrode is an alloy/dealloying reaction mechanism, the generated lithium-silicon alloy is easy to generate huge volume expansion relative to silicon, so that the electrode material is easy to gradually break and pulverize in the repeated lithiation/delithiation process, the integrity of the electrode material is remarkably deteriorated, and the initiation performance is rapidly deteriorated. At the same time, considering the relatively low intrinsic electronic conductivity of silicon anode material (10)-3S·cm-1) Further, the initial coulomb efficiency is low and the rate capability is not poor. Moreover, considering the effect of interfacial stress, the silicon negative electrode is liable to be gradually separated from the contact with the current collector during long-term cycling, resulting in the presence of active material and current collectorThe effective electrical contact is broken. These factors together lead to slower electrochemical kinetics and poorer electrochemical properties of the silicon negative electrode. Therefore, a new silicon negative electrode material needs to be developed to achieve better cycle life, rate capability and coulombic efficiency.
Composite carbon nanomaterials are a common method of improving silicon negative electrodes, such as carbon nanotubes, graphene, amorphous carbon, etc. The carbon nano material has excellent conductivity, can improve the poor conductivity of the silicon cathode, has good mechanical property, can relieve the volume expansion of the silicon cathode to a great extent, and further improves the cycling stability of the silicon cathode. Then, the conventional carbon nanomaterial-silicon composite electrode material tends to suffer from the following problems: (1) the traditional mechanical mixing mode is difficult to realize the tight combination of the carbon nano material and the silicon, so that the effective electric contact between the carbon nano material and the silicon is less, and the conductive network cannot be optimized; (2) the carbon nano material-silicon composite material is lack of effective interconnection, so that the mechanical strength is low, the carbon nano material-silicon composite material is easy to fall off from the surface of a current collector, and the long-term periodic performance of the carbon nano material-silicon composite material is seriously influenced; (3) the traditional preparation method is difficult to realize that the carbon nano material is uniformly coated on the silicon surface, so that the conductivity and the lithium ion diffusion path of the carbon nano material cannot be optimized.
Disclosure of Invention
The invention aims to solve the technical problems of large volume change, too low intrinsic electronic conductivity, poor interface binding force, poor long-period stability, low coulombic efficiency and the like in the charging and discharging processes of the conventional silicon cathode material; and provides a carbon-carbon nanotube-silicon nanoparticle and a method for preparing the same.
The invention uses the chemical vapor deposition method to coat the carbon layer on the surface of the silicon nano-particles in situ in advance, thereby improving the interconnection between the silicon and the carbon nano-tubes and realizing sufficient electric contact. Then, a floating catalyst method is utilized to prepare a mutually cross-linked carbon nano tube network on the surface of the carbon nano tube. The preparation method of the carbon-carbon nanotube-silicon nanoparticle has the advantages of quick preparation, good dispersibility, controllable size and good electrochemical performance, and is a lithium battery cathode material with wide application prospect.
The carbon-carbon nanotube-silicon nanoparticle is prepared by performing chemical vapor deposition on silicon nanoparticles in a mixed atmosphere of argon and hydrogen, depositing a carbon layer through plasma vapor deposition, and growing a carbon nanotube by a floating catalyst method.
The preparation method of the carbon-carbon nanotube-silicon nanoparticle comprises the following steps:
step one, carrying out chemical vapor deposition on silicon nanoparticles in a mixed atmosphere of argon and hydrogen;
secondly, depositing a carbon layer by plasma gas phase;
and step three, growing the carbon nano tube by using a floating catalyst method to obtain the carbon-carbon nano tube-silicon nano particle.
Further defining the process parameters of the chemical vapor deposition in the step one as follows: the flow rate of the mixed gas is 5 sccm-100 sccm, the gas pressure is 0.1 Torr-1 Torr, the hydrogen gas accounts for 5% of the total volume of the mixed gas, the temperature is 350-900 ℃, and the deposition time is 1 min-30 min.
Further, the plasma vapor deposition of the carbon layer in the second step is completed by the following steps: raising the temperature until the temperature reaches 350-500 ℃, and introducing CO2And CH4Gas of, wherein Ar-H2The gas flow of the mixed gas is controlled to be 1 sccm-100 sccm, and CO is2The gas flow rate of (C) is controlled to be 1 sccm-100 sccm, CH4The gas flow rate is controlled to be 1 sccm-100 sccm, the pressure of the total gas is adjusted to be 0.1 Torr-1 Torr, and then deposition is carried out for 1 min-30 min under the condition that the power of a plasma radio frequency power supply is 10W-200W, Ar-H2The hydrogen in the mixed gas accounts for 5 percent of the total volume of the mixed gas.
Further, the growing of the carbon nanotubes by using the floating catalyst method in the third step is completed by the following steps: with Ar-H2The mixed gas is taken as carrier gas, the catalyst is carried into the reaction area for 1min to 20min, and then CO is introduced2And CH4Gas of Ar-H2The gas flow of the mixed gas is controlled to be 1 sccm-100 sccm, and CO is2Gas flow control ofAt 1 sccm-100 sccm, CH4The gas flow rate is controlled to be 1 sccm-100 sccm, the pressure of the total gas is adjusted to be 0.1 Torr-1 Torr, then deposition is carried out for 1 min-30 min under the condition that the power of a plasma radio frequency power supply is 50W-500W, the radio frequency power supply is closed after deposition is finished, and Ar-H2Is cooled to room temperature.
Further limiting, the catalyst solution is prepared from nitrate and a solvent, and the concentration is 0.1 mmol/L-10 mmol/L; wherein the nitrate is one of cobalt nitrate, nickel nitrate and ferric nitrate, and the solvent is one of absolute ethyl alcohol, isopropanol and glycerol.
The carbon-carbon nanotube-silicon nanoparticles or the carbon-carbon nanotube-silicon nanoparticles prepared by the method are used as a negative electrode material of a lithium battery.
The method can realize the tight combination between the carbon nano tube and the carbon layer by in-situ preparation, buffer the volume expansion effect of silicon, and the carbon nano tubes which are mutually crosslinked can form a conductive network, thereby being beneficial to the quick conduction of the composite material.
According to the invention, the prefabricated carbon layer is deposited, so that the tight combination between the carbon nano material and the silicon nano particles is realized, the volume expansion of the silicon nano particles in the lithiation/delithiation process can be effectively relieved, and the better cycle performance is realized;
according to the invention, on the basis of the prefabricated carbon layer, the mutually-crosslinked carbon nanotube network is deposited by adopting a floating catalyst method, so that the conductivity and the lithium ion diffusion path of the composite electrode material can be optimized, the rapid charge and discharge of the composite electrode material are facilitated, and the good coulombic efficiency and rate capability are further realized.
The invention can realize the low-temperature and rapid deposition of the carbon nano material on the silicon nano surface by the aid of the plasma radio frequency power supply.
The carbon-carbon nanotube-silicon nanoparticle composite electrode material prepared by the invention has the advantages of quick preparation, good dispersibility, controllable size and good electrochemical performance, and is a lithium battery cathode material with wide application prospect.
Detailed Description
Example 1:
the preparation method of the carbon-carbon nanotube-silicon nanoparticle in the embodiment is performed according to the following steps:
step one, placing silicon nano particles in chemical vapor deposition equipment, vacuumizing, and then placing the silicon nano particles in Ar-H2Heating the mixed gas (hydrogen accounts for 5% of the total volume of the mixed gas) with the flow rate of 50sccm and the gas pressure of 0.5Torr for 50min to 500 ℃, depositing for 10min after heating, and taking out;
secondly, placing the mixture in a plasma sputtering device, heating the mixture until the temperature reaches a set temperature (500 ℃), and introducing CO2And CH4Gas, control of Ar-H2The gas flow rate of the mixed gas (hydrogen accounts for 5% of the total volume of the mixed gas) is 10sccm, and CO is controlled2The gas flow of (1 sccm) and CH control4The gas flow of the gas is 90sccm, the pressure of the total gas is adjusted to be 1Torr, and then deposition is carried out for 10min under the condition that the power of a plasma radio frequency power supply is 200W;
step three, then Ar-H2The mixed gas is used as carrier gas, the catalyst is carried by the carrier gas and enters the reaction zone for 15min, and CO is introduced2And CH4Gas, control of Ar-H2The gas flow rate of the mixed gas (hydrogen accounts for 5% of the total volume of the mixed gas) is 50sccm, and CO is controlled2The gas flow of (2) is 20sccm, CH is controlled4The gas flow of the gas is 30sccm, the pressure of the total gas is adjusted to be 1Torr, then deposition is carried out for 25min under the condition that the power of a plasma radio frequency power supply is 350W, the radio frequency power supply is closed after the deposition is finished, and Ar-H2Cooling to room temperature under the atmosphere to obtain carbon-carbon nanotube-silicon nanoparticles;
wherein the concentration of the catalyst solution in the third step is 0.5 mmol.L-1Cobalt nitrate is dissolved in isopropanol and stirred for 0.5h by magnetic force.
The carbon-carbon nanotube-silicon nanoparticles prepared in example 1 were used as a negative electrode, 1MLiPF6The capacity of the electrolyte solution was maintained at 73% after a 200-week cycle stability test, and thus it can be seen that the carbon-carbon nanotube-silicon nanoparticles according to the present inventionIs an ideal negative electrode material of the lithium battery.
Example 2:
the preparation method of the carbon-carbon nanotube-silicon nanoparticle in the embodiment is performed according to the following steps:
step one, placing silicon nano particles in chemical vapor deposition equipment, vacuumizing, and then placing the silicon nano particles in Ar-H2Heating the mixed gas (hydrogen accounts for 5 percent of the total volume of the mixed gas) under the conditions of the flow rate of 20sccm and the gas pressure of 0.5Torr for 45min to 450 ℃, depositing for 10min after the heating is finished, and taking out;
secondly, placing the mixture in a plasma sputtering device, heating the mixture until the temperature reaches the set temperature (450 ℃), and introducing CO2And CH4Gas, control of Ar-H2The gas flow rate of the mixed gas (hydrogen accounts for 5% of the total volume of the mixed gas) is 20sccm, and CO is controlled2The gas flow of (1 sccm) and CH control4The gas flow of the gas is 90sccm, the pressure of the total gas is adjusted to be 0.5Torr, and then deposition is carried out for 5min under the condition that the power of a plasma radio frequency power supply is 200W;
step three, then Ar-H2The mixed gas (hydrogen accounts for 5% of the total volume of the mixed gas) is used as carrier gas, the catalyst is carried into the reaction zone by the carrier gas for 5min, and CO is introduced2And CH4Gas, control of Ar-H2The gas flow of the mixed gas is 50sccm, and CO is controlled2The gas flow of (2) is 10sccm, CH is controlled4The gas flow of the gas is 90sccm, the pressure of the total gas is adjusted to be 1Torr, then deposition is carried out for 5min under the condition that the power of a plasma radio frequency power supply is 400W, the radio frequency power supply is closed after the deposition is finished, and Ar-H2Cooling to room temperature under the atmosphere to obtain carbon-carbon nanotube-silicon nanoparticles;
wherein the concentration of the catalyst solution in the third step is 0.5 mmol.L-1Nickel nitrate is dissolved in glycerol and stirred for 0.5h by magnetic force.
The carbon-carbon nanotube-silicon nanoparticles prepared in example 2 were used as a negative electrode, 1MLiPF6For the electrolyte, the capacity is still 75% after the circulation stability test of 200 weeks, therebyTherefore, the carbon-carbon nanotube-silicon nanoparticle is an ideal negative electrode material of the lithium battery.

Claims (10)

1. The carbon-carbon nanotube-silicon nanoparticle is characterized in that the electrode material is prepared by carrying out chemical vapor deposition on silicon nanoparticles in a mixed atmosphere of argon and hydrogen, depositing a carbon layer in a plasma vapor deposition manner, and growing the carbon nanotube by a floating catalyst method.
2. The method of claim 1, wherein the method comprises the steps of:
step one, carrying out chemical vapor deposition on silicon nanoparticles in a mixed atmosphere of argon and hydrogen;
secondly, depositing a carbon layer by plasma gas phase;
and step three, growing the carbon nano tube by using a floating catalyst method to obtain the carbon-carbon nano tube-silicon nano particle.
3. The method of claim 2, wherein the chemical vapor deposition process comprises the following steps: the flow rate of the mixed gas is 5 sccm-100 sccm, the gas pressure is 0.1 Torr-1 Torr, the hydrogen gas accounts for 5% of the total volume of the mixed gas, the temperature is 350-900 ℃, and the deposition time is 1 min-30 min.
4. The method of claim 2, wherein the chemical vapor deposition process comprises the following steps: the flow rate of the mixed gas was 50sccm, the gas pressure was 0.5Torr, hydrogen gas was 5% of the total volume of the mixed gas, the temperature was 500 ℃, and the deposition time was 10 min.
5. The method of claim 2, wherein the plasma vapor deposition of the carbon layer in the second step is performed byThe steps are completed: raising the temperature until the temperature reaches 350-900 ℃, and introducing CO2And CH4Gas of, wherein Ar-H2The gas flow of the mixed gas is controlled to be 1 sccm-100 sccm, and CO is2The gas flow rate of (C) is controlled to be 1 sccm-100 sccm, CH4The gas flow rate is controlled to be 1 sccm-100 sccm, the pressure of the total gas is adjusted to be 0.1 Torr-1 Torr, and then deposition is carried out for 1 min-30 min under the condition that the power of a plasma radio frequency power supply is 10W-200W, Ar-H2The hydrogen in the mixed gas accounts for 5 percent of the total volume of the mixed gas.
6. The method of claim 2, wherein the plasma vapor deposition of the carbon layer in the second step is performed by: heating until the temperature reaches 500 ℃, introducing CO2And CH4Gas of, wherein Ar-H2The gas flow rate of the mixed gas is controlled to be 10sccm, CO2The gas flow rate of (2) is controlled at 1sccm, CH4The gas flow rate is controlled to be 90sccm, the pressure of the total gas is adjusted to be 1Torr, and then deposition is carried out for 10min under the condition that the power of a plasma radio frequency power supply is 200W, wherein Ar-H is2The hydrogen in the mixed gas accounts for 5 percent of the total volume of the mixed gas.
7. The method of claim 2, wherein the growing of the carbon nanotubes by the floating catalyst method in the third step is performed by: with Ar-H2Mixed gas as carrier gas, Ar-H2Hydrogen in the mixed gas accounts for 5 percent of the total volume of the mixed gas, the catalyst is carried into a reaction zone for 1-20 min, and then CO is introduced2And CH4Gas of Ar-H2The gas flow of the mixed gas is controlled to be 1 sccm-100 sccm, and CO is2The gas flow rate of (C) is controlled to be 1 sccm-100 sccm, CH4The gas flow rate is controlled to be 1 sccm-100 sccm, the pressure of the total gas is adjusted to be 0.1 Torr-1 Torr, then deposition is carried out for 1 min-30 min under the condition that the power of a plasma radio frequency power supply is 50W-500W, and after the deposition is finished, the injection is closedFrequency power supply at Ar-H2Is cooled to room temperature.
8. The method of claim 2, wherein the growing of the carbon nanotubes by the floating catalyst method in the third step is performed by: with Ar-H2Mixed gas as carrier gas, Ar-H2Hydrogen in the mixed gas accounts for 5% of the total volume of the mixed gas, the catalyst is carried into a reaction zone for 15min, and then Ar-H is added2The gas flow rate of the mixed gas is controlled to be 50sccm, CO2The gas flow rate of (2) is controlled at 20sccm, CH4The gas flow rate is controlled at 30sccm, the pressure of the total gas is adjusted to be 1Torr, then deposition is carried out for 1 min-30 min under the condition that the power of a plasma radio frequency power supply is 30W, the radio frequency power supply is closed after the deposition is finished, and Ar-H2Is cooled to room temperature.
9. The method of claim 7, wherein the catalyst solution is prepared from nitrate and a solvent, and the concentration of the catalyst solution is 0.1mmol/L to 10 mmol/L; wherein the nitrate is one of cobalt nitrate, nickel nitrate and ferric nitrate, and the solvent is one of ethanol, isopropanol and glycerol.
10. The carbon-carbon nanotube-silicon nanoparticle as set forth in claim 1 is used as a negative electrode material for lithium batteries.
CN201911221776.5A 2019-12-03 2019-12-03 Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof Pending CN110880592A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911221776.5A CN110880592A (en) 2019-12-03 2019-12-03 Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911221776.5A CN110880592A (en) 2019-12-03 2019-12-03 Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN110880592A true CN110880592A (en) 2020-03-13

Family

ID=69730086

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911221776.5A Pending CN110880592A (en) 2019-12-03 2019-12-03 Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110880592A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111525121A (en) * 2020-05-10 2020-08-11 兰溪致德新能源材料有限公司 Silicon anode material with villus structure and preparation method thereof
CN112234197A (en) * 2020-09-08 2021-01-15 中南大学 Amorphous carbon-silicon-carbon nanofiber-graphite composite material and preparation method and application thereof
CN111370663B (en) * 2020-03-18 2021-05-25 浙江锂宸新材料科技有限公司 Porous silicon @ amorphous carbon/carbon nanotube composite material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025219A (en) * 2016-06-24 2016-10-12 中天储能科技有限公司 Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof
CN106058256A (en) * 2016-07-19 2016-10-26 复旦大学 Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery
CN108565408A (en) * 2018-01-10 2018-09-21 电子科技大学 A kind of lithium ion battery negative material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025219A (en) * 2016-06-24 2016-10-12 中天储能科技有限公司 Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof
CN106058256A (en) * 2016-07-19 2016-10-26 复旦大学 Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery
CN108565408A (en) * 2018-01-10 2018-09-21 电子科技大学 A kind of lithium ion battery negative material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
周静主编: "《近代材料科学研究技术进展》", 31 December 2012, 武汉理工大学出版社 *
李爱农，刘钰如主编: "《工程材料及应用》", 31 January 2019, 华中科技大学出版社 *
罗金华等: "三维纳米硅/多孔碳的储锂性能", 《电池》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111370663B (en) * 2020-03-18 2021-05-25 浙江锂宸新材料科技有限公司 Porous silicon @ amorphous carbon/carbon nanotube composite material and preparation method and application thereof
CN111525121A (en) * 2020-05-10 2020-08-11 兰溪致德新能源材料有限公司 Silicon anode material with villus structure and preparation method thereof
CN112234197A (en) * 2020-09-08 2021-01-15 中南大学 Amorphous carbon-silicon-carbon nanofiber-graphite composite material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN110299516B (en) Preparation method of carbon nanotube array loaded lithium titanate flexible electrode material
CN107946576B (en) High-rate graphite negative electrode material, preparation method thereof and lithium ion battery
CN109616630B (en) Silicon-carbon composite material with uniform carbon film and vertical graphene double coating, preparation method thereof and application of silicon-carbon composite material in lithium ion battery
CN108649190A (en) Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application
CN104103821B (en) The preparation method of silicon-carbon cathode material
CN110880592A (en) Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof
CN112421048A (en) Method for preparing graphite-coated nano-silicon lithium battery negative electrode material at low cost
CN108417800B (en) Graphene-coated graphite/metal composite powder negative electrode material and preparation method thereof
CN114122352A (en) Silicon-carbon negative electrode material for inducing silicon deposition by doping porous carbon and preparation method thereof
CN112820847A (en) Silicon-based negative electrode material and preparation method thereof, lithium ion battery and electric appliance
CN113690424B (en) Carbon-tin-silicon negative electrode material of lithium ion battery and preparation method thereof
CN111370656B (en) Silicon-carbon composite material and preparation method and application thereof
CN114824200A (en) Hierarchical carbon-coated silicon micro-nano composite anode material and preparation method and application thereof
Ma et al. Hierarchical porous and lithiophilic CuMn current collector for advanced lithium metal batteries
CN110474037B (en) Preparation method of porous silicon-carbon composite negative electrode material
CN115207303A (en) High-energy quick-charging graphite cathode composite material and preparation method thereof
Hao et al. Ionic liquid electrodeposition of 3D germanium–acetylene black–Ni foam nanocomposite electrodes for lithium-ion batteries
CN109301224B (en) Preparation method and application of silicon-based composite negative electrode material of lithium ion battery
CN113258069B (en) Negative electrode active material, method for preparing same, negative electrode, and secondary battery
Lang et al. Study on the electrochemical performance of lead-acid battery with micro/nanostructure tetrabasic lead sulfate prepared via sol-gel method
CN114039042B (en) Silicon oxide negative electrode material with artificial SEI film, and preparation method and application thereof
CN116154141B (en) Silicon-carbon negative electrode material with watermelon-like structure and preparation method thereof
CN113594440B (en) Lithium ion battery anode material with multistage conductive structure and preparation method thereof
CN115249815A (en) Method for rapidly preparing lithium-philic three-dimensional carbon conductive framework
CN115959671A (en) Porous carbon network modified silicon monoxide composite negative electrode material and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200313