CN108039465B - Composite electrode material, preparation method and application thereof - Google Patents

Composite electrode material, preparation method and application thereof Download PDF

Info

Publication number
CN108039465B
CN108039465B CN201711249261.7A CN201711249261A CN108039465B CN 108039465 B CN108039465 B CN 108039465B CN 201711249261 A CN201711249261 A CN 201711249261A CN 108039465 B CN108039465 B CN 108039465B
Authority
CN
China
Prior art keywords
electrode material
composite electrode
silicon particles
sodium alginate
material according
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
Application number
CN201711249261.7A
Other languages
Chinese (zh)
Other versions
CN108039465A (en
Inventor
张慧
连崑
李维汉
宗平
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.)
RESEARCH INSTITUTE OF XI'AN JIAOTONG UNIVERSITY IN SUZHOU
Original Assignee
RESEARCH INSTITUTE OF XI'AN JIAOTONG UNIVERSITY IN SUZHOU
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 RESEARCH INSTITUTE OF XI'AN JIAOTONG UNIVERSITY IN SUZHOU filed Critical RESEARCH INSTITUTE OF XI'AN JIAOTONG UNIVERSITY IN SUZHOU
Priority to CN201711249261.7A priority Critical patent/CN108039465B/en
Publication of CN108039465A publication Critical patent/CN108039465A/en
Application granted granted Critical
Publication of CN108039465B publication Critical patent/CN108039465B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/362—Composites
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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 provides a preparation method of a composite electrode material, which comprises the following steps: uniformly dispersing carbon nano tubes, silicon particles and water-soluble organic matters in water, adding sodium alginate for crosslinking to form hydrogel, and freeze-drying a crosslinked product; carbonizing the product at 350-600 ℃ under protective atmosphere to obtain the composite electrode material. The microstructure of the composite electrode material prepared by the invention is three-dimensional grid, and silicon particles and carbon nanotubes are embedded in a lamellar structure. The invention also provides application of the composite electrode material in preparing lithium ion batteries. The invention takes the skeleton structure of the sodium alginate hydrogel as a template, adopts a simple and efficient method to prepare the composite electrode material with good conductivity, has adjustable morphology and good cycling stability.

Description

Composite electrode material, preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a composite electrode material and a preparation method and application thereof.
Background
Today, the conventional energy source is increasingly scarce, and development of a secondary battery with high specific energy is urgent, in which a silicon anode has attracted great attention due to high specific capacity. However, this limits its use in practical production due to the large volume expansion (400%) during charge and discharge.
At present, the main method for solving the problem of silicon negative electrode failure is to provide an expansion space for the expansion of silicon, but the prior art is complex in process and difficult to realize, and is extremely easy to pollute the environment and difficult to realize large-scale industrialized production. In addition, it has been found that the stress effect is not a major factor affecting the performance of lithium ion batteries when the silicon particle size reaches below 150 nm. However, to date, no large-scale, low-cost and industrialized preparation technology exists in the research and development results of high-capacity, high-performance, long-service-life and low-cost silicon-based lithium ion rechargeable battery electrodes. Therefore, finding a negative electrode material that has a simple preparation process and good lithium ion storage performance becomes a key for developing a lithium ion battery.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a composite electrode material, a preparation method and application thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
in one aspect, the invention provides a method for preparing a composite electrode material, comprising the steps of:
(1) Uniformly mixing carbon nano tubes, silicon particles and water-soluble organic matters in water, and then adding sodium alginate to uniformly mix to obtain a mixed solution;
(2) Adding a metal compound into the mixed solution obtained in the step (1), uniformly mixing, then adding a slow release agent, standing and freeze-drying;
(3) And (3) heating the product obtained in the step (2) to a high temperature in a protective atmosphere to carbonize, so as to obtain the composite electrode material.
Further, in the step (1), the particle diameter of the silicon particles is 50nm to 1. Mu.m, preferably 50 to 100nm. That is, the silicon particles are nano silicon particles or micro silicon particles.
Further, in step (1), the water-soluble organic substance is polyvinylpyrrolidone, which acts as a dispersant.
Further, in the step (1), the mass ratio of the carbon nanotubes, the silicon particles and the water-soluble organic matter is 0.5-2:1:1. And forming a mixed solution, namely a precursor solution, by adjusting the ratio of the carbon nano tube to the silicon particles and the ratio of the carbon nano tube to the sodium alginate.
Further, in the step (2), the metal compound is selected from one or more of calcium carbonate, basic copper carbonate, copper hydroxide, nickel nitrate and ferric nitrate. And (3) forming gels with different crosslinking degrees by adjusting the proportion of the metal compound, the slow release agent and the substances in the step (1).
Further, in the step (1), the mass ratio of the sodium alginate to the carbon nano tube and the silicon particles is 5-50:3.
further, in step (2), the mass ratio of the metal compound to the silicon particles is 5-60:4.
Further, in the step (2), the mass ratio of the slow release agent to the solute in the mixed solution in the step (1) is 3:1-15.
Preferably, in the step (2), the slow release agent is gluconolactone and/or acetic acid.
Further, in the step (3), the protective atmosphere is one or more of nitrogen, helium and argon.
In the step (2), after the slow release agent is added, the slow release agent slowly releases hydrogen ions, the hydrogen ions react with the metal compound to release corresponding metal ions, and the metal ions are crosslinked with sodium alginate to form hydrogel, and in the process of forming the hydrogel, the carbon nano tube and the silicon particles are wrapped in the sodium alginate hydrogel. In the gelation process, the solid-solid interfaces between different amounts of carbon nanotubes and silicon particles are different, and the microstructure of the composite material can be adjusted and the performance of the composite electrode is finally affected by adjusting the addition amount of the substance containing metal ions and the slow release agent.
Further, in the step (2), the product is placed in a room temperature environment for standing, the sodium alginate undergoes a gelation reaction, and the solution is gradually solidified into hydrogel.
Further, the product obtained in the step (2) is kept stand for 6-24 hours. Preferably, the resting time is 12-24 hours, more preferably 24 hours.
Further, the product obtained in the step (2) is freeze-dried for 12-24 hours. Preferably, the drying time is 24 hours.
Further, in step (3), the product obtained in step (2) is heated to 350-600 ℃ under a protective atmosphere, and the material is carbonized to form a silicon carbon compound. Preferably, in step (3), the composite hydrogel is heated to 400 ℃ under a protective atmosphere and carbonized completely.
On the other hand, the invention also provides a composite electrode material prepared by the method, wherein the microstructure of the composite electrode material is three-dimensional grid-shaped, and the inside of the structure is supported by silicon particles and carbon nano tubes to form a framework.
In a further aspect, the invention also provides application of the composite electrode material in preparation of lithium ion batteries.
By means of the scheme, the invention has the following advantages:
the invention provides a method for preparing a composite electrode material, which adopts sodium alginate to prepare the composite electrode material with regular structure and stable property, has adjustable size and can be produced in a large scale. According to the method, the carbon nano tube is used as a conductive network, so that on one hand, the conductivity of the whole composite electrode can be improved, and on the other hand, the carbon nano tube has certain toughness, and the formed network can relieve the problem of volume expansion of silicon. In addition, sodium alginate is used as a hydrogel raw material, nano metal particles are obtained after carbonization treatment, and the conductivity of the electrode material is improved. Therefore, the composite electrode material prepared by the method can improve the cycling stability of the electrode, and can be widely applied to the fields of electroplating, electrolysis, solidification crystallization and the like.
Brief description of the drawings
FIG. 1 is an SEM image of the freeze-dried product of example 1 of the present invention;
FIG. 2 is an enlarged view of a portion of the structure of FIG. 1;
FIG. 3 is an SEM image of the carbonized product of example 1 of the present invention;
FIG. 4 is an XRD pattern of the composite electrode material of example 1 of the present invention;
FIG. 5 is a graph showing the electrochemical properties of the composite electrode material according to example 1 of the present invention
FIG. 6 is an SEM image of the freeze-dried product of example 2 of the present invention;
FIG. 7 is an SEM image of the carbonized product of example 2 of the present invention;
FIG. 8 is an enlarged view of a portion of the structure of FIG. 7;
FIG. 9 is an SEM image of the freeze-dried product of example 3 of the present invention;
FIG. 10 is an SEM image of the carbonized product of example 3 of the present invention;
FIG. 11 is an enlarged view of a portion of the structure of FIG. 10;
FIG. 12 is an SEM image of the freeze-dried product of example 4 of the present invention having a sodium alginate mass of 0.5 g;
FIG. 13 is an SEM image of carbonized product with a mass of 0.5g of sodium alginate in example 4 of the present invention;
fig. 14 is an enlarged view of a part of the structure in fig. 13;
FIG. 15 is an SEM image of the freeze-dried product of example 4 of the present invention when the mass of sodium alginate is 5 g;
FIG. 16 is an SEM image of carbonized product with a mass of 5g of sodium alginate in example 4 of the present invention;
fig. 17 is an enlarged view of a part of the structure in fig. 16;
FIG. 18 is an SEM image of the freeze-dried product of example 5 of the present invention;
FIG. 19 is an SEM image of the carbonized product of example 5 of the present invention;
fig. 20 is an enlarged view of a part of the structure in fig. 19;
FIG. 21 is an SEM image of the lyophilized product of example 6 of the present invention;
FIG. 22 is an SEM image of the carbonized product of example 6 of the present invention;
fig. 23 is an enlarged view of a part of the structure in fig. 22;
FIG. 24 is a diagram showing a crosslinked structure according to example 7 of the present invention;
FIG. 25 is a diagram showing a carbonized material obtained in example 7 of the present invention;
FIG. 26 is an XRD pattern after carbonization in example 7 of the present invention;
FIG. 27 is a diagram showing a crosslinked structure according to example 8 of the present invention;
FIG. 28 is a diagram showing a carbonized material obtained in example 8 of the present invention;
FIG. 29 is an XRD pattern after carbonization in example 8 of the present invention;
FIG. 30 is an SEM image of carbonized material of example 9 of the present invention;
FIG. 31 is an SEM image of carbonized material of example 9 of the present invention;
FIG. 32 is an SEM image of the carbonized material of example 9 of the present invention.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. It is to be understood that the following examples are for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml water according to the mass ratio of 100mg to 100mg, then performing ultrasonic dispersion for 30min by using an ultrasonic crusher, adding 2g of sodium alginate, continuously mechanically stirring for 2h, adding 1.5g of copper hydroxide, mechanically stirring for 30min, adding 3g of gluconolactone, uniformly stirring, standing for 24h, and freeze-drying for 24h. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. Fig. 1 and 2 show SEM images of the material, and it can be seen from the figures that the freeze-dried material has a three-dimensional grid shape, and the average thickness of the layer sheet is 8-10 μm. Fig. 3 is an SEM image of a carbonized material at 400 ℃, from which it can be seen that the carbonized material can still maintain a three-dimensional network structure well. FIG. 4 is an XRD pattern showing that the carbonized material is composed mainly of Si+Cu+Cu 2 O composition. FIG. 5 is a graph showing the electrochemical performance, the left ordinate represents the specific discharge capacity, and the abscissa represents the number of cycles, and it can be seen from the graph that 45 cycles are cycled at a current density of C/2 (1C=4200mA/g)The discharge specific capacity of 623mAh/g is still obtained.
Example 2
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml water according to the mass ratio of 200mg:100mg, then performing ultrasonic dispersion for 30min by using an ultrasonic crusher, adding 2g of sodium alginate, continuing to mechanically stir for 2h, adding 1.5g of copper hydroxide, mechanically stirring for 30min, adding 3g of gluconolactone, uniformly stirring, standing for 24h, and freeze-drying for 24h. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. Fig. 6-8 show SEM characterization results of the obtained material, compared with example 1, the three-dimensional grid structure is unchanged with the increase of the quality of the nano silicon powder, and the carbonized sheet has copper elementary particles with the particle size of 1-10 μm, and the carbonized sheet still maintains a better three-dimensional grid structure.
Example 3
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml of water according to the mass ratio of 100mg to 200mg, then performing ultrasonic dispersion for 30min by using an ultrasonic crusher, adding 2g of sodium alginate, continuing to mechanically stir for 2h, adding 1.5g of copper hydroxide, mechanically stirring for 30min, adding 3g of gluconolactone, uniformly stirring, standing for 24h, and freeze-drying for 24h. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. Fig. 9-11 show SEM characterization results of the obtained material, the three-dimensional grid structure of the composite electrode material is changed into a honeycomb structure along with the increase of the mass of the carbon nano tube, the diameter of the holes is 2-20 μm, the surface of the structure and the surface of the holes are uniformly distributed with copper simple substance particles, and the particle size is 1-3 μm.
Example 4
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml water according to the mass ratio of 100mg:200mg, then ultrasonically dispersing for 30min by using an ultrasonic crusher, and then adding 0.5g sodium alginate to obtain a mixed solution. In addition, nano silicon powder (particle size is 50-100 nm), carbon nano tubes and polyvinylpyrrolidone are mixed in 100ml of water according to the mass ratio of 100mg to 200mg, then ultrasonic dispersion is carried out for 30min by an ultrasonic crusher, and then 5g of sodium alginate is added to obtain a mixed solution. The two mixed solutions were treated as follows: after continuing mechanical stirring for 2 hours, 1.5g of copper hydroxide is added for mechanical stirring, 3g of gluconolactone is taken out after 30 minutes, and after uniform stirring, standing is carried out for 24 hours, and then freeze drying is carried out for 24 hours. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. Fig. 12-14 show SEM characterization results of the material when sodium alginate is 0.5g, and fig. 15-17 show SEM characterization results of the material when sodium alginate is 5g, when sodium alginate is 0.5g, no holes appear in the structure, and copper simple substance particles with the particle size of 1-2 μm are uniformly distributed on the surface of the structure. When the mass of sodium alginate is increased to 5g, holes appear in the structure, copper simple substance particles with the size of 2-20 mu m distributed on the surfaces of the structure and the holes are reduced, the particle size is increased, and the particle size is 1-6 mu m.
Example 5
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml of water according to the mass ratio of 100mg to 200mg, then ultrasonically dispersing for 30min by using an ultrasonic crusher, adding 2g of sodium alginate, continuing to mechanically stir for 2h, adding 1.5g of copper hydroxide, mechanically stirring for 30min, taking out, adding 3g of acetic acid, uniformly stirring, standing for 24h, and freeze-drying for 24h. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. Fig. 18-20 show that the pores in the structure and the copper elementary particles on the surface of the structure substantially disappear after acetic acid is used as a slow release agent to obtain the SEM characterization result of the material.
Example 6
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml of water according to the mass ratio of 100mg to 200mg, then performing ultrasonic dispersion for 30min by using an ultrasonic crusher, adding 2g of sodium alginate, continuing to mechanically stir for 2h, adding 0.5g of calcium carbonate, mechanically stirring for 30min, taking out, adding 1g of glucolactone, uniformly stirring, standing for 24h, and freeze-drying for 24h. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. Fig. 21-23 show SEM characterization results of the obtained material, wherein the microstructure is a three-dimensional grid structure, the spacing between layers is 1-2 μm, the structure is loose and the surface of the layers is smooth when calcium carbonate is used as a cross-linking agent.
EXAMPLE 7 Ni (NO) 3 ) 2
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml water according to the mass ratio of 100mg to 100mg, then performing ultrasonic dispersion for 30min by using an ultrasonic crusher, adding 1g of sodium alginate, continuously mechanically stirring for 2h, adding 0.25g of nickel nitrate, uniformly stirring, standing for 24h, and then performing freeze drying for 24h. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. FIG. 24 is a pictorial view of a cross-linked material from which it is known to exhibit bulk characteristics. Fig. 25 is a schematic representation of the carbonized material, from which it is understood that the material can still macroscopically maintain the bulk structure of the bulk material. Fig. 26 is an XRD pattern of the metal removed using nitric acid after carbonization of the material, which can be seen as silicon particles, meeting the requirements of lithium ion batteries for electrode materials.
Example 8- -Fe (NO) 3 ) 3
Mixing nano silicon powder (particle size is 50-100 nm), carbon nano tube and polyvinylpyrrolidone in 100ml water according to the mass ratio of 100mg to 100mg, then performing ultrasonic dispersion for 30min by using an ultrasonic crusher, adding 1g of sodium alginate, continuously mechanically stirring for 2h, adding 0.25g of ferric nitrate, mechanically stirring uniformly, standing for 24h, and freeze-drying for 24h. And heating the freeze-dried product to 400 ℃ in a tube furnace for carbonization, wherein the heating time is 2h, and nitrogen is used as a protective gas in the tube furnace. And taking out the silicon-carbon composite electrode material after the furnace is cooled to room temperature. FIG. 27 is a pictorial view of a cross-linked material, from which it is known that the material exhibits bulk characteristics. Fig. 28 is a schematic representation of the carbonized material, from which it is seen that the material can still macroscopically maintain the bulk structure of the bulk material. FIG. 29 is an XRD pattern of a carbonized material with a primary phase of Si+Fe-C.
EXAMPLE 9 micron silicon
Mixing micrometer silica powder (particle size of 1 μm), carbon nanotube and polyvinylpyrrolidone in 100ml water according to mass ratio of 100mg:100mg, ultrasonically dispersing for 30min by using an ultrasonic crusher, adding 1g sodium alginate, mechanically stirring for 2h, adding 0.25g copper hydroxide, mechanically stirring for 30min, taking out, adding 0.5g gluconolactone, uniformly stirring, standing for 24h, and freeze-drying for 24h. Fig. 30-32 show SEM characterization results of the obtained material, in which the microstructure is pea-shaped, the structure is loose and rank, and the surface of the lamellar sheet is smooth when copper hydroxide is used as a cross-linking agent.

Claims (9)

1. The preparation method of the composite electrode material is characterized by comprising the following steps of:
(1) Uniformly dispersing the carbon nano tube, the silicon particles and the water-soluble organic matters in water, and then adding sodium alginate to uniformly mix to obtain a mixed solution;
(2) Adding a metal compound into the mixed solution obtained in the step (1), uniformly mixing, then adding a slow release agent, standing and freeze-drying, wherein the slow release agent is gluconolactone and/or acetic acid;
(3) And (3) heating the product obtained in the step (2) to carbonize in a protective atmosphere to obtain the composite electrode material.
2. The method for producing a composite electrode material according to claim 1, characterized in that: in step (1), the silicon particles have a particle diameter of 50nm to 1 μm.
3. The method for producing a composite electrode material according to claim 1, characterized in that: in the step (1), the water-soluble organic matter is polyvinylpyrrolidone.
4. The method for producing a composite electrode material according to claim 1, characterized in that: in the step (1), the metal compound is one or more selected from calcium carbonate, basic copper carbonate, copper hydroxide, nickel nitrate and ferric nitrate.
5. The method for producing a composite electrode material according to claim 1, characterized in that: in the step (1), the mass ratio of the carbon nano tube to the silicon particles to the water-soluble organic matter is 0.5-2:1:1.
6. The method for producing a composite electrode material according to claim 1, characterized in that: in the step (1), the ratio of the sodium alginate to the sum of the mass of the carbon nano tube and the mass of the silicon particles is 5-50:3.
7. the method for producing a composite electrode material according to claim 1, characterized in that: in the step (2), the mass ratio of the metal compound to the silicon particles is 5-60:4.
8. A composite electrode material prepared according to the method of any one of claims 1-7.
9. Use of the method for preparing a composite electrode material according to any one of claims 1 to 7 for preparing a lithium ion battery.
CN201711249261.7A 2017-12-01 2017-12-01 Composite electrode material, preparation method and application thereof Active CN108039465B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711249261.7A CN108039465B (en) 2017-12-01 2017-12-01 Composite electrode material, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711249261.7A CN108039465B (en) 2017-12-01 2017-12-01 Composite electrode material, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108039465A CN108039465A (en) 2018-05-15
CN108039465B true CN108039465B (en) 2023-09-01

Family

ID=62095066

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711249261.7A Active CN108039465B (en) 2017-12-01 2017-12-01 Composite electrode material, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108039465B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108987702B (en) * 2018-07-16 2021-03-12 西安交通大学苏州研究院 Integrated electrode material based on composite aerogel and preparation and application thereof
CN109802175B (en) * 2019-01-22 2021-02-26 吴海燕 Preparation method of gel-state electrolyte of sodium ion battery
CN109830668B (en) * 2019-02-28 2021-09-03 昆明理工大学 Method for preparing lithium ion battery silicon-carbon negative electrode material by adopting carbon nano tube
CN111146421B (en) * 2019-12-26 2022-03-18 宁德新能源科技有限公司 Negative electrode material, and electrochemical device and electronic device comprising same
CN111146434A (en) * 2019-12-26 2020-05-12 宁德新能源科技有限公司 Negative electrode material, and electrochemical device and electronic device comprising same
CN111146424B (en) * 2019-12-30 2023-06-06 上海交通大学 Metal sulfide/carbon composite material, and preparation method and application thereof
CN113943158B (en) * 2021-12-20 2022-07-19 杭州德海艾科能源科技有限公司 Preparation method of graphite felt for flow battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102267684A (en) * 2010-06-03 2011-12-07 中国科学院化学研究所 Metallic nano particle/ carbon composite material and preparation method and application thereof
CN104282894A (en) * 2013-07-08 2015-01-14 北京化工大学 Preparation method of porous Si/C composite microsphere
CN107093707A (en) * 2017-03-17 2017-08-25 西安交通大学苏州研究院 Combination electrode material and its preparation method and application
CN107134565A (en) * 2017-03-17 2017-09-05 西安交通大学苏州研究院 Combination electrode material and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102267684A (en) * 2010-06-03 2011-12-07 中国科学院化学研究所 Metallic nano particle/ carbon composite material and preparation method and application thereof
CN104282894A (en) * 2013-07-08 2015-01-14 北京化工大学 Preparation method of porous Si/C composite microsphere
CN107093707A (en) * 2017-03-17 2017-08-25 西安交通大学苏州研究院 Combination electrode material and its preparation method and application
CN107134565A (en) * 2017-03-17 2017-09-05 西安交通大学苏州研究院 Combination electrode material and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
基于海藻酸双金属氧化物气凝胶的锂离子电池负极材料的研究;孙欣;《中国优秀硕士学位论文全文数据库》(第第2期期);第B016-596页 *

Also Published As

Publication number Publication date
CN108039465A (en) 2018-05-15

Similar Documents

Publication Publication Date Title
CN108039465B (en) Composite electrode material, preparation method and application thereof
CN109273680B (en) Porous silicon-carbon negative electrode material, preparation method thereof and lithium ion battery
US9666863B2 (en) Nano silicon-carbon composite material and preparation method thereof
CN109742383B (en) Sodium ion battery hard carbon negative electrode material based on phenolic resin and preparation method and application thereof
CN107611416B (en) Silicon-carbon composite material, preparation method and application thereof
CN112542577B (en) Nano bismuth/nitrogen-doped carbon foam nanosheet two-dimensional composite material and preparation method and application thereof
CN104103821B (en) The preparation method of silicon-carbon cathode material
CN107732174B (en) Carbon-coated LiFePO of lithium ion battery4Preparation method of/CNTs composite positive electrode material
CN111313029A (en) Closely-combined high-performance silicon/graphitized carbon composite material with hollow structure and preparation method and application thereof
CN109473649B (en) Composite negative electrode material of sodium-ion battery and preparation method thereof
CN109003827B (en) Preparation method and application of spongy graphene/nickel-cobalt sulfide composite material
Jiang et al. A diatomite-derived N-doped carbon aerogel with 98% sulfur loading for the enhancement of Li–S battery performance
CN108807903B (en) Preparation method of composite modified lithium battery negative electrode material for lithium battery
CN110299514B (en) Core-shell structure silicon-carbon negative electrode material, preparation method and negative electrode plate
CN113178571B (en) Hierarchical porous Fe3Se4@ NC @ CNTs composite material and preparation method and application thereof
CN112320784B (en) Sulfur-doped iron-nitrogen-carbon supercapacitor electrode material and preparation method and application thereof
CN112289966A (en) Lithium-sulfur battery positive electrode material, and preparation method and application thereof
CN110299511B (en) Nano composite negative plate, preparation method thereof and lithium ion battery
CN115036152B (en) Hollow spherical boron-carbon-nitrogen material and preparation method thereof
CN110844908A (en) Preparation method of high-performance silicon carbon-graphite composite negative electrode material for lithium ion battery
CN109786722B (en) Method for producing electrochemically active material
JP2017174817A (en) Method for controllable synthesis of carbon-based battery electrode material
CN107658457B (en) SiO for fused salt electrolysis2-Gc/C composite electrode and preparation method thereof
Chen et al. One-step synthesis of uniformly distributed SiO x–C composites as stable anodes for lithium-ion batteries
CN112259735A (en) Method for integrally preparing hollow silicon-carbon particles of lithium battery by using sand mill and extruder

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