CN110729460A - Nano-silicon composite lithium-supplementing negative electrode material of lithium ion battery and preparation method and application thereof - Google Patents

Nano-silicon composite lithium-supplementing negative electrode material of lithium ion battery and preparation method and application thereof Download PDF

Info

Publication number
CN110729460A
CN110729460A CN201910941095.XA CN201910941095A CN110729460A CN 110729460 A CN110729460 A CN 110729460A CN 201910941095 A CN201910941095 A CN 201910941095A CN 110729460 A CN110729460 A CN 110729460A
Authority
CN
China
Prior art keywords
lithium
ion battery
lithium ion
nano
negative electrode
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.)
Granted
Application number
CN201910941095.XA
Other languages
Chinese (zh)
Other versions
CN110729460B (en
Inventor
张立君
陈慧龙
段恒志
***
曹雁超
王念贵
王瑛
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.)
Shandong Yuhuang New Energy Technology Co Ltd
Original Assignee
Shandong Yuhuang New Energy Technology Co Ltd
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 Shandong Yuhuang New Energy Technology Co Ltd filed Critical Shandong Yuhuang New Energy Technology Co Ltd
Priority to CN201910941095.XA priority Critical patent/CN110729460B/en
Publication of CN110729460A publication Critical patent/CN110729460A/en
Application granted granted Critical
Publication of CN110729460B publication Critical patent/CN110729460B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4242—Regeneration of electrolyte or reactants
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • 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 provides a lithium ion battery nano-silicon composite lithium-supplementing negative electrode material and a preparation method and application thereof. The composite lithium-supplement cathode material is prepared by adopting a chemical deposition method and electrostatic spinning, the obtained composite lithium-supplement cathode material for the lithium ion battery has stable performance and high safety, uniform lithium supplement can be realized, the first efficiency and the energy density of the lithium ion battery are improved, the conductivity of the lithium ion battery is effectively improved, and the long cycle and the excellent rate performance of the lithium ion battery are ensured. The preparation method of the composite lithium-supplement cathode material is simple and easy to realize.

Description

Nano-silicon composite lithium-supplementing negative electrode material of lithium ion battery and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a nano-silicon composite lithium-supplement negative electrode material of a lithium ion battery, and a preparation method and application thereof.
Background
The lithium ion battery has the characteristics of high working voltage, large specific energy, small volume, light weight, long cycle life and the like, so that the lithium ion battery becomes the focus of development and competition of the automobile industry. With the continuous development of lithium ion batteries in the fields of portable electronic devices, electric bicycles and electric automobiles, the requirements on the energy density and other properties of the lithium ion batteries are higher and higher.
The traditional commercial lithium ion battery mainly adopts a graphite carbon material as a negative electrode material, however, the theoretical specific capacity of the commercial graphite negative electrode material is only 372mAh/g, and the theoretical specific capacity of silicon is up to 4200mAh/g, which is far higher than that of commercial graphite, and the silicon has wide sources, low cost and environmental friendliness, so the silicon is always paid attention by researchers and is one of the next-generation lithium ion battery negative electrode materials with the most potential. However, silicon undergoes severe volume expansion (300-400%) during charging and discharging, so that the silicon bears a large mechanical action force in charging and discharging cycles and gradually becomes powder and collapses, connection between an active material and a current collector is affected, and electron transmission is not facilitated; on the other hand, a solid electrolyte interface film formed between the silicon-based material and the electrolyte is gradually thickened, so that the capacity of the lithium battery is not improved, and the cycle performance of the lithium battery is reduced rapidly. Therefore, the research and development of a lithium ion battery cathode material with high capacity and long cycle life is a technical problem to be solved urgently in the industry at present.
In addition, in the first charge and discharge process of the lithium ion battery, the electrode material and the electrolyte react at a solid-liquid phase interface to form a Solid Electrolyte Interface (SEI) passive film, and a large amount of active lithium ions are consumed, so that the first irreversible coulombic efficiency is low, and the energy density and performance of the battery are reduced.
Lithium metal or a lithium-containing compound is added into the negative electrode material, so that lithium ions consumed by the first charge and discharge of the lithium ion battery can be supplemented, the first efficiency of the battery is improved, lithium consumed by the formation of an SEI film is supplemented, the transmission rate of the lithium ions is improved, and the cycle performance of the battery is improved. At present, common lithium supplement methods include in-situ doping lithium supplement, electrochemical lithium supplement and chemical lithium pre-supplement methods, but the methods have high requirements on the environment and potential safety hazards such as flammability and the like, so that the further popularization and application of each method are limited.
CN103346325B discloses a lithium ion battery cathode material, which comprises graphene, nano silicon particles distributed in a graphene lamellar structure, and a reticulated carbon material distributed between the graphene lamellar structure and the nano silicon particles. In the lithium ion battery cathode material provided by the invention, the carbon materials of the graphene sheet layer and the network structure are closely contacted with the nano silicon particles, so that the conductivity of the material is improved; meanwhile, in the charging and discharging process, the huge volume change of silicon particles can be effectively buffered, so that the lithium ion battery cathode material provided by the invention has better cycle performance. However, since this material does not contain lithium ions, the material cannot provide a lithium-supplementing effect despite its high capacity remaining ratio after cycling.
CN109301188A discloses a highly dispersed lithium supplement material for a lithium ion battery, which is a graphene sheet with metal lithium particles uniformly dispersed on the surface; the surface of the metal lithium particle is coated with a carbon layer; the lithium ion battery lithium supplement material can obviously improve the first charge-discharge efficiency of the lithium ion battery and the cycle performance of the battery, but because metal lithium particles are all distributed on the surface of graphene, lithium on the surface of flaky graphene can be crushed and separated from the surface of graphene in the cycle process, so that lithium death is caused, and the effectiveness of the material is greatly reduced.
Disclosure of Invention
The invention aims to solve the problems, provides a preparation method of a lithium ion battery nano-silicon composite lithium-supplement cathode material, develops a lithium ion battery nano-silicon composite lithium-supplement cathode material with good dispersion of metal lithium and nano-silicon and excellent electrochemical performance, and effectively improves the conductivity of the material and the production efficiency of the cathode material prepared by the method.
In one aspect, the invention provides a lithium ion battery nano-silicon composite lithium-supplementing negative electrode material, which comprises fibrous graphene, nano-silicon particles deposited inside and on the surface of the graphene, and metal lithium particles distributed inside and on the surface of the graphene, wherein at least one part of the surface of the graphene is coated with a carbon layer.
Further, the mass ratio of the graphene to the nano silicon particles to the lithium metal particles is as follows: 1: 0.1-5: 0.01 to 0.3.
On the other hand, the invention provides a preparation method of the lithium ion battery nano-silicon composite lithium-supplement negative electrode material, which comprises the following steps:
(1) under the protection of inert gas, performing chemical vapor deposition on nano silicon particles on graphene by using silane gas;
(2) adding the material obtained in the step (1) and an organic lithium solution into an alkane solvent, and uniformly dispersing to obtain a dispersion liquid;
(3) carrying out electrostatic spinning treatment on the dispersion liquid obtained in the step (2) to obtain a spinning substance;
(4) and (4) calcining the spinning substance obtained in the step (3) at high temperature by taking alkane gas as a carbon source to coat carbon, so as to obtain the nano-silicon composite lithium-supplement cathode material of the lithium ion battery.
Further, in the step (1), the inert gas is one of nitrogen and argon or a combination thereof;
the silane gas is any one of monosilane, trichlorosilane and dichlorosilane;
the chemical vapor deposition is thermal chemical vapor deposition.
Preferably, the thermal chemical vapor deposition is performed by: introducing silane gas into a furnace containing graphene, heating to thermally decompose the silane gas, and depositing nano silicon particles on the surface of the graphene;
the silane gas is introduced at the flow rate of 1.0-2.0L/min for 30-60 min; the heating temperature is 700-1000 ℃.
Further, in the step (2), the alkane solvent is an n-ethane solution or a cyclohexane solution;
the organic lithium solution is one or a mixture of more than two of butyl lithium, tert-butyl lithium or phenyl lithium;
the concentration of the organic lithium solution is 0.1-5 mol/L.
Preferably, the specific operation of step (2) is as follows: under inert atmosphere, adding the material obtained in the step (1) and an organic lithium solution into an alkane solvent, and sequentially carrying out ultrasonic dispersion and magnetic stirring;
the inert atmosphere is one or the combination of nitrogen and argon;
the ultrasonic dispersion time is 90-180 min, the magnetic stirring temperature is 40-80 ℃, and the time is 12-24 h.
Further, in the step (3), the voltage of the electrostatic spinning is 10-20 KV, the spraying speed is 0.01-0.03 mm/s, and the diameter of a spinning nozzle used for the electrostatic spinning is 0.6-1.6 mm.
Further, in the step (4), the heating rate of the high-temperature calcination is 1-5 ℃/min, the calcination temperature is 600-900 ℃, and the calcination time is 2-4 h.
In one embodiment, the preparation method of the lithium ion battery negative electrode composite lithium-supplement negative electrode material comprises the following steps:
(1) placing 10g of graphene in a tubular furnace, introducing monosilane gas into the reaction furnace at a low flow rate of 1.0L/min under the protection of nitrogen, heating to 750 ℃ to thermally decompose the monosilane gas, wherein the introduction time is 30min, and depositing on the surface of the graphene to generate nano silicon particles;
(2) adding the material obtained in the step (1) and 100mL of butyl lithium with the concentration of 1mol/L into 30mL of a cyclohexane solution, and performing ultrasonic dispersion for 2 hours and magnetic stirring at 40 ℃ for 24 hours to obtain a dispersion liquid;
(3) putting the dispersion liquid obtained in the step (2) into a disposable injector, putting the disposable injector into an electrostatic spinning instrument, performing electrostatic spinning by adopting a spinning nozzle with the diameter of 1.0mm, wherein the voltage of the electrostatic spinning is 20KV, the spraying speed is 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning liquid, and drying to obtain a spinning substance;
(4) and (4) removing the spinning substance obtained in the step (3), placing the spinning substance in a muffle furnace, heating the muffle furnace to 700 ℃ at the speed of 5 ℃/min, and carrying out carbon coating for 3 hours by using methane gas as a carbon source to obtain the material, namely the lithium ion battery nano-silicon composite lithium supplement negative electrode material.
On the other hand, the invention also provides the application of the composite lithium-supplement negative electrode material or the method in the preparation of the lithium ion battery.
The invention has the beneficial effects that:
(1) according to the composite lithium supplement cathode material, the fibrous graphene is used as a carrier, the nano silicon particles and the metal lithium particles are distributed in the graphene and on the surface of the graphene, and part of the nano silicon and the metal lithium particles are distributed in the graphene, so that the problem that a silicon simple substance directly contacts with an electrolyte to generate a violent reaction in the circulation of a lithium ion battery is effectively solved, the phenomenon of lithium death caused by separation of carbon on the surface of the graphene in the circulation process of the battery is avoided, and the lithium supplement can be continuously provided in the circulation process of the battery. The graphene and the nano silicon particles are in close contact, so that the conductivity of the graphene is improved, the first efficiency and the capacity retention rate of the lithium ion battery are improved by cooperation with the metal lithium particles, and the long cycle performance of the lithium ion battery is improved.
(2) The composite lithium-supplement cathode material is prepared by adopting a chemical deposition method and electrostatic spinning, the lithium-supplement cathode material distributed with the nano silicon particles and the metal lithium particles is obtained, the obtained lithium-supplement cathode material for the lithium ion battery has stable performance and high safety, uniform lithium supplement can be realized, the first efficiency and the energy density of the lithium ion battery are improved, the conductivity of the lithium ion battery is effectively improved, and the long cycle and the excellent rate performance of the lithium ion battery are ensured.
(4) The preparation method of the composite lithium-supplement cathode material is simple and easy to realize.
Drawings
Fig. 1 is a partial schematic view of a scanning electron microscope of the composite lithium supplement negative electrode material prepared in embodiment 1 of the present invention.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. It will be apparent, however, to one skilled in the art, that the present application may be practiced without one or more of these specific details. In other instances, well-known features of the art have not been described in order to avoid obscuring the present application.
The starting materials in the following examples are all commercially available, unless otherwise specified.
Example 1
A lithium ion battery nano-silicon composite lithium-supplementing negative electrode material comprises: the graphene comprises fibrous graphene, nano silicon particles deposited inside the graphene and on the surface of the graphene, and metal lithium particles distributed between the graphene and the nano silicon particles, wherein carbon layers are coated on the surfaces of the nano silicon particles and the metal lithium particles on the surface of the graphene.
The preparation method of the lithium ion battery nano-silicon composite lithium-supplement cathode material comprises the following steps:
(1) placing 10g of graphene in a tube furnace, introducing monosilane gas into the furnace at a low flow rate of 1.0L/min under the protection of nitrogen, heating to 750 ℃ to thermally decompose the monosilane gas, wherein the introduction time is 30min, and depositing on the surface of the graphene to generate nano silicon particles;
(2) adding the material obtained in the step (1) and 100mL of butyl lithium with the concentration of 1mol/L into 30mL of a cyclohexane solution, and performing ultrasonic dispersion for 2 hours and magnetic stirring at 40 ℃ for 24 hours to obtain a dispersion liquid;
(3) putting the dispersion liquid obtained in the step (2) into a disposable injector, putting the disposable injector into an electrostatic spinning instrument, performing electrostatic spinning by adopting a spinning nozzle with the diameter of 1.0mm, wherein the voltage of the electrostatic spinning is 20KV, the spraying speed is 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning liquid, and drying to obtain a spinning substance;
(4) and (4) removing the spinning substance obtained in the step (3), placing the spinning substance in a muffle furnace, heating the muffle furnace to 700 ℃ at the speed of 5 ℃/min, and carrying out carbon coating for 3 hours by using methane gas as a carbon source to obtain the material, namely the lithium ion battery nano-silicon composite lithium supplement negative electrode material.
Comparative example 1
Comparative example 1 provides a graphene sheet having metallic lithium particles dispersed on the surface thereof, prepared by the following method:
(1) adding 1ml of n-butyllithium solution and 1mg of graphene sheets into 30ml of cyclohexane solution in a nitrogen environment, then placing the solution into a high-pressure reaction kettle, and screwing the reaction kettle tightly; (2) putting the high-pressure reaction kettle in an oil bath at the temperature of 110 ℃ for reaction for 20 hours; (3) cleaning the product after reaction by adopting tetrahydrofuran solution for 3 times, and vacuumizing and drying; (4) and putting the cleaned product in a muffle furnace at 700 ℃, and carrying out carbon coating for 3 hours by using methane gas as a carbon source to obtain the material, namely the high-dispersion lithium supplement material for the sheet lithium ion battery.
Test examples
And (3) electrochemical performance testing: and spraying the composite lithium-supplement negative electrode material prepared in the embodiment 1 on a copper foil current collector to prepare a lithium ion battery negative electrode sheet, and respectively obtaining the lithium ion batteries with the numbers of A-D. And adding the lithium supplement material prepared in the comparative example 1 into the silicon-based negative electrode material, uniformly mixing, spraying the mixture on a copper foil current collector to prepare a lithium ion battery negative electrode plate, and obtaining the lithium ion battery with the serial number E. And the first charge-discharge efficiency, the capacity residual rate after 100 weeks of circulation and the energy density of the battery are measured on each example lithium ion battery, wherein the battery data are average values of at least 5 parallel battery test results, and the obtained results are shown in table 1.
The method for testing the first charge-discharge coulombic efficiency refers to the national standard GB/T243334-2009 graphite cathode material for lithium ion batteries; the cycle performance test method is as follows: charging the battery to an upper limit voltage at 23 ℃ with a constant current of 0.5C, then performing constant voltage charging, and cutting off the current of 0.05C; standing for 10min, discharging to 2.7V at constant current of 0.5C, and measuring to obtain initial discharge capacity C of the battery0(ii) a After standing for 10min, repeating the above steps for 100 weeks, and performing continuous charge-discharge test to obtain the capacity C of the battery after 100 cycles1. The capacity remaining rate of the battery after 100 cycles was calculated according to the following formula: capacity remaining rate ═ C1/C0X 100%. The battery energy density measurement method is as follows: charging the current to the upper limit voltage at 23 ℃ with a constant current of 0.5C, then converting to constant voltage charging, and cutting off the current by 0.05C; standing for 10min, discharging to 2.7V at constant current of 0.5C, and measuring the discharge capacity of the battery; after standing for 10min, the above steps were repeated 3 times, and the average value of the 3 discharge capacities was calculated. The different types of batteries were weighed using an electronic balance. The 23 ℃ cell energy density was calculated as follows: battery energy density is the average capacity of discharge x median voltage/weight of the battery. Internal resistance measurements were made using an ac impedance meter on the cell after 100 cycles. And (4) carrying out constant current charge and discharge test on the assembled simulation battery by adopting a Land battery test system. The test current is 100mA/g, and the voltage range is 0-3V. The first reversible capacity and discharge capacity were obtained.
TABLE 1 Battery Performance test results
Figure BDA0002222926070000071
As can be seen from table 1, the lithium-supplement negative electrode material provided in example 1 can effectively improve the first charge-discharge efficiency and cycle performance of the battery, and particularly, the capacity retention rate of the battery after 100 cycles can reach 99% at most. In the battery of the lithium-supplement negative electrode material provided by the comparative example 1, although the first charge-discharge coulombic efficiency and the capacity residual rate after 100-week circulation are improved, the improvement effect is not as good as that of the example 1, in addition, the energy density, the first reversible capacity and the discharge capacity of the example 1 are obviously higher than those of the comparative example 1, and the internal resistance of the battery of the example 1 is obviously lower than that of the comparative example 1, which shows that the composite lithium-supplement negative electrode material provided by the invention can obviously improve the conductivity of the active material of the battery.
Example 2
A lithium ion battery nano-silicon composite lithium-supplementing negative electrode material comprises: the graphene comprises fibrous graphene, nano silicon particles deposited inside the graphene and on the surface of the graphene, and metal lithium particles distributed between the graphene and the nano silicon particles, wherein carbon layers are coated on the surfaces of the nano silicon particles and the metal lithium particles on the surface of the graphene.
The preparation method of the lithium ion battery nano-silicon composite lithium-supplement cathode material comprises the following steps:
(1) placing 10g of graphene in a tubular furnace, introducing trichlorosilane gas into the furnace at a low flow rate of 1.0L/min under the protection of nitrogen, heating to 750 ℃ to thermally decompose the trichlorosilane gas, wherein the introduction time is 30min, and depositing on the surface of the graphene to generate nano silicon particles;
(2) adding the material obtained in the step (1) and 100mL of tert-butyl lithium with the concentration of 1mol/L into 30mL of a cyclohexane solution, performing ultrasonic dispersion for 2 hours, performing magnetic stirring at 40 ℃ for 24 hours, and uniformly mixing to obtain a dispersion liquid;
(3) putting the dispersion liquid obtained in the step (2) into a disposable injector, putting the disposable injector into an electrostatic spinning instrument, performing electrostatic spinning by adopting a spinning nozzle with the diameter of 0.6mm, wherein the voltage of the electrostatic spinning is 20KV, the spraying speed is 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning liquid, and drying to obtain a spinning substance;
(4) and (4) removing the spinning substance obtained in the step (3), placing the spinning substance in a muffle furnace, heating the muffle furnace to 700 ℃ at the speed of 5 ℃/min, and carrying out carbon coating for 3 hours by using methane gas as a carbon source to obtain the material, namely the lithium ion battery nano-silicon composite lithium supplement negative electrode material.
Example 3
A lithium ion battery nano-silicon composite lithium-supplementing negative electrode material comprises: the graphene comprises fibrous graphene, nano silicon particles deposited inside the graphene and on the surface of the graphene, and metal lithium particles distributed between the graphene and the nano silicon particles, wherein carbon layers are coated on the surfaces of the nano silicon particles and the metal lithium particles on the surface of the graphene.
The preparation method of the lithium ion battery nano-silicon composite lithium-supplement cathode material comprises the following steps:
(1) placing 10g of graphene in a tubular furnace, introducing dichlorosilane gas into the furnace at a low flow rate of 1.0L/min under the protection of nitrogen, heating to 750 ℃ to thermally decompose the dichlorosilane gas, wherein the introduction time is 30min, and depositing on the surface of the graphene to generate nano silicon particles;
(2) under the nitrogen environment, adding the material obtained in the step (1) and 100mL of phenyl lithium with the concentration of 1mol/L into 30mL of a cyclohexane solution, performing ultrasonic dispersion for 2 hours, performing magnetic stirring at 40 ℃ for 24 hours, and uniformly mixing to obtain a dispersion liquid;
(3) putting the spinning solution obtained in the step (2) into a disposable injector, putting the disposable injector into an electrostatic spinning instrument, performing electrostatic spinning by adopting a spinning head with the diameter of 1.6mm, wherein the voltage of the electrostatic spinning is 20KV, the spraying speed is 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning solution, and drying to obtain a spinning substance;
(4) and (4) removing the spinning substance obtained in the step (3), placing the spinning substance in a muffle furnace, heating the muffle furnace to 700 ℃ at the speed of 5 ℃/min, and carrying out carbon coating for 3 hours by using methane gas as a carbon source to obtain the material, namely the lithium ion battery nano-silicon composite lithium supplement negative electrode material.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. A lithium ion battery nano silicon composite lithium-supplementing cathode material is characterized in that: the composite lithium-supplementing negative electrode material comprises fibrous graphene, nano silicon particles deposited inside and on the surface of the graphene and metal lithium particles distributed inside and on the surface of the graphene, wherein at least one part of the surface of the graphene is coated with a carbon layer.
2. The lithium ion battery nano-silicon composite lithium-supplementing negative electrode material of claim 1, characterized in that: the mass ratio of the graphene to the nano silicon particles to the metal lithium particles is 1: 0.1-5: 0.01 to 0.3.
3. The preparation method of the lithium ion battery nano-silicon composite lithium-supplement negative electrode material as claimed in claim 1 or 2, characterized by comprising the following steps: the method comprises the following steps:
(1) carrying out chemical vapor deposition on nano silicon particles on graphene by using silane gas under the protection of inert gas;
(2) adding the material obtained in the step (1) and an organic lithium solution into an alkane solvent, and uniformly dispersing to obtain a dispersion liquid;
(3) carrying out electrostatic spinning treatment on the dispersion liquid obtained in the step (2) to obtain a spinning substance;
(4) and (4) calcining the spinning substance obtained in the step (3) at high temperature by taking alkane gas as a carbon source to coat carbon, so as to obtain the nano-silicon composite lithium-supplement cathode material of the lithium ion battery.
4. The preparation method of the lithium ion battery nano-silicon composite lithium-supplementing negative electrode material according to claim 3, characterized by comprising the following steps: in the step (1), the inert gas is one or a combination of nitrogen and argon;
preferably, the silane gas is any one of monosilane, trichlorosilane and dichlorosilane;
preferably, the chemical vapor deposition is thermal chemical vapor deposition.
5. The preparation method of the lithium ion battery nano-silicon composite lithium-supplementing negative electrode material according to claim 4, characterized in that: the specific operation of the thermal chemical vapor deposition is as follows: introducing silane gas into a furnace containing graphene, heating to thermally decompose the silane gas, and depositing nano silicon particles on the surface of the graphene;
preferably, the flow rate of the silane gas is 1.0-2.0L/min, and the time of the silane gas is 30-60 min; the heating temperature is 700-1000 ℃.
6. The preparation method of the lithium ion battery nano-silicon composite lithium-supplementing negative electrode material according to claim 3, characterized by comprising the following steps: in the step (2), the alkane solvent is an n-ethane solution or a cyclohexane solution;
preferably, the organic lithium solution is one or a mixture of more than two of butyl lithium, tert-butyl lithium or phenyl lithium;
preferably, the concentration of the organic lithium solution is 0.1-5 mol/L.
7. The preparation method of the lithium ion battery nano-silicon composite lithium-supplementing negative electrode material according to any one of claims 3 to 6, characterized by comprising the following steps: the specific operation of the step (2) is as follows: under inert atmosphere, adding the material obtained in the step (1) and an organic lithium solution into an alkane solvent, and sequentially carrying out ultrasonic dispersion and magnetic stirring;
preferably, the inert atmosphere is one or a combination of nitrogen and argon;
preferably, the ultrasonic dispersion time is 90-180 min, the magnetic stirring temperature is 40-80 ℃, and the time is 12-24 h.
8. The preparation method of the lithium ion battery nano-silicon composite lithium-supplementing negative electrode material according to claim 3, characterized by comprising the following steps: in the step (3), the voltage of the electrostatic spinning is 10-20 KV, the spraying speed is 0.01-0.03 mm/s, and the diameter of a spinning nozzle used for the electrostatic spinning is 0.6-1.6 mm.
9. The preparation method of the lithium ion battery nano-silicon composite lithium-supplementing negative electrode material according to claim 3, characterized by comprising the following steps: in the step (4), the heating rate of the high-temperature calcination is 1-5 ℃/min, the calcination temperature is 600-900 ℃, and the calcination time is 2-4 h.
10. Use of the composite lithium-supplementing negative electrode material according to claim 1 or 2 or the method according to any one of claims 3 to 9 in the preparation of a lithium ion battery.
CN201910941095.XA 2019-09-30 2019-09-30 Nano silicon composite lithium supplementing negative electrode material of lithium ion battery and preparation method and application thereof Active CN110729460B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910941095.XA CN110729460B (en) 2019-09-30 2019-09-30 Nano silicon composite lithium supplementing negative electrode material of lithium ion battery and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910941095.XA CN110729460B (en) 2019-09-30 2019-09-30 Nano silicon composite lithium supplementing negative electrode material of lithium ion battery and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110729460A true CN110729460A (en) 2020-01-24
CN110729460B CN110729460B (en) 2023-06-30

Family

ID=69218586

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910941095.XA Active CN110729460B (en) 2019-09-30 2019-09-30 Nano silicon composite lithium supplementing negative electrode material of lithium ion battery and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110729460B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021179219A1 (en) * 2020-03-11 2021-09-16 宁德新能源科技有限公司 Anode plate and manufacturing method therefor, battery using anode plate, and electronic apparatus
CN113422009A (en) * 2021-06-01 2021-09-21 广东工业大学 Lithium ion battery cathode material and preparation method and application thereof
CN116169255A (en) * 2021-11-25 2023-05-26 湖南中科星城石墨有限公司 Silicon-carbon negative electrode material of lithium ion battery, and preparation method and application thereof
WO2024050756A1 (en) * 2022-09-08 2024-03-14 宁德时代新能源科技股份有限公司 Silicon-carbon negative electrode material and preparation method therefor, secondary battery and electric device

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102306757A (en) * 2011-08-26 2012-01-04 上海交通大学 Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material
US20130047423A1 (en) * 2011-08-29 2013-02-28 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing positive electrode active material for lithium ion battery
US20130108920A1 (en) * 2011-11-01 2013-05-02 Isalah O. Oladeji Composite electrodes for lithium ion battery and method of making
CN103346325A (en) * 2013-06-28 2013-10-09 中国科学院宁波材料技术与工程研究所 Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
US20130295439A1 (en) * 2012-05-04 2013-11-07 Charan Masarapu Battery cell engineering and design to reach high energy
CN103730643A (en) * 2012-10-16 2014-04-16 海洋王照明科技股份有限公司 Silicon and graphene composite electrode material, preparing method thereof and lithium ion battery
CN104577084A (en) * 2015-01-20 2015-04-29 深圳市贝特瑞新能源材料股份有限公司 Nano silicon composite negative electrode material for lithium ion battery, preparation method and lithium ion battery
WO2015068195A1 (en) * 2013-11-05 2015-05-14 株式会社日立製作所 Negative electrode active material for lithium ion secondary cell, method for manufacturing negative electrode active material for lithium ion secondary cell, and lithium ion secondary cell
US20160118652A1 (en) * 2014-10-27 2016-04-28 Industrial Technology Research Institute Anode material for lithium ion battery and lithium ion battery including the same
CN105914343A (en) * 2016-07-11 2016-08-31 洛阳力容新能源科技有限公司 Lithium ion battery negative plate as well as preparation method and application thereof and lithium ion battery
CN106067547A (en) * 2016-08-10 2016-11-02 深圳市贝特瑞新能源材料股份有限公司 Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite
WO2017083804A1 (en) * 2015-11-13 2017-05-18 SiNode Systems, Inc. Graphene-encapsulated electroactive material for use in a lithium ion electrochemical cell
CN106876689A (en) * 2017-03-24 2017-06-20 中航锂电（洛阳）有限公司 A kind of nitrogen-doped graphene silicon composite cathode material and preparation method thereof, lithium ion battery
CN107346822A (en) * 2017-04-25 2017-11-14 山东玉皇新能源科技有限公司 A kind of method that solvent-thermal method prepares graphene silicon composite cathode material
CN107492645A (en) * 2017-08-09 2017-12-19 深圳市金牌新能源科技有限责任公司 One kind aoxidizes sub- 3 SiC 2/graphite alkene composite and preparation method thereof
CN107611391A (en) * 2017-09-05 2018-01-19 珠海格力电器股份有限公司 A kind of lithium metal secondary battery negative pole and preparation method thereof
WO2018032974A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Method of preparing material of negative electrode of lithium ion battery
WO2018032977A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Manufacturing method of negative-electrode material for lithium-ion battery
WO2018032975A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Manufacturing method of lithium-ion battery negative-electrode material effectively buffering volume change effect of silicon
KR20180039984A (en) * 2016-10-11 2018-04-19 재단법인대구경북과학기술원 Silicon-graphene composites, method for preparing the same and lithium ion battery comprising the same
CN108511758A (en) * 2018-03-23 2018-09-07 安普瑞斯（无锡）有限公司 A kind of aqueous benefit lithium additive of cathode and preparation method thereof
US20190020017A1 (en) * 2016-01-04 2019-01-17 Airbus Singapore Private Limited Group iv-vi compound graphene anode with catalyst
CN109301188A (en) * 2018-09-11 2019-02-01 天津市捷威动力工业有限公司 A kind of lithium ion battery of high dispersive mends lithium material and preparation method thereof
CN109309194A (en) * 2017-07-26 2019-02-05 中能中科（天津）新能源科技有限公司 It is modified without cathode of lithium, preparation method and contains its lithium ion battery
CN109546100A (en) * 2018-10-16 2019-03-29 中航锂电（洛阳）有限公司 A kind of silicon-carbon composite film electrode and lithium ion battery

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102306757A (en) * 2011-08-26 2012-01-04 上海交通大学 Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material
US20130047423A1 (en) * 2011-08-29 2013-02-28 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing positive electrode active material for lithium ion battery
US20130108920A1 (en) * 2011-11-01 2013-05-02 Isalah O. Oladeji Composite electrodes for lithium ion battery and method of making
US20130295439A1 (en) * 2012-05-04 2013-11-07 Charan Masarapu Battery cell engineering and design to reach high energy
CN103730643A (en) * 2012-10-16 2014-04-16 海洋王照明科技股份有限公司 Silicon and graphene composite electrode material, preparing method thereof and lithium ion battery
CN103346325A (en) * 2013-06-28 2013-10-09 中国科学院宁波材料技术与工程研究所 Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
WO2015068195A1 (en) * 2013-11-05 2015-05-14 株式会社日立製作所 Negative electrode active material for lithium ion secondary cell, method for manufacturing negative electrode active material for lithium ion secondary cell, and lithium ion secondary cell
US20160118652A1 (en) * 2014-10-27 2016-04-28 Industrial Technology Research Institute Anode material for lithium ion battery and lithium ion battery including the same
CN104577084A (en) * 2015-01-20 2015-04-29 深圳市贝特瑞新能源材料股份有限公司 Nano silicon composite negative electrode material for lithium ion battery, preparation method and lithium ion battery
WO2017083804A1 (en) * 2015-11-13 2017-05-18 SiNode Systems, Inc. Graphene-encapsulated electroactive material for use in a lithium ion electrochemical cell
US20190020017A1 (en) * 2016-01-04 2019-01-17 Airbus Singapore Private Limited Group iv-vi compound graphene anode with catalyst
CN105914343A (en) * 2016-07-11 2016-08-31 洛阳力容新能源科技有限公司 Lithium ion battery negative plate as well as preparation method and application thereof and lithium ion battery
CN106067547A (en) * 2016-08-10 2016-11-02 深圳市贝特瑞新能源材料股份有限公司 Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite
WO2018032975A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Manufacturing method of lithium-ion battery negative-electrode material effectively buffering volume change effect of silicon
WO2018032974A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Method of preparing material of negative electrode of lithium ion battery
WO2018032977A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Manufacturing method of negative-electrode material for lithium-ion battery
KR20180039984A (en) * 2016-10-11 2018-04-19 재단법인대구경북과학기술원 Silicon-graphene composites, method for preparing the same and lithium ion battery comprising the same
CN106876689A (en) * 2017-03-24 2017-06-20 中航锂电（洛阳）有限公司 A kind of nitrogen-doped graphene silicon composite cathode material and preparation method thereof, lithium ion battery
CN107346822A (en) * 2017-04-25 2017-11-14 山东玉皇新能源科技有限公司 A kind of method that solvent-thermal method prepares graphene silicon composite cathode material
CN109309194A (en) * 2017-07-26 2019-02-05 中能中科（天津）新能源科技有限公司 It is modified without cathode of lithium, preparation method and contains its lithium ion battery
CN107492645A (en) * 2017-08-09 2017-12-19 深圳市金牌新能源科技有限责任公司 One kind aoxidizes sub- 3 SiC 2/graphite alkene composite and preparation method thereof
CN107611391A (en) * 2017-09-05 2018-01-19 珠海格力电器股份有限公司 A kind of lithium metal secondary battery negative pole and preparation method thereof
CN108511758A (en) * 2018-03-23 2018-09-07 安普瑞斯（无锡）有限公司 A kind of aqueous benefit lithium additive of cathode and preparation method thereof
CN109301188A (en) * 2018-09-11 2019-02-01 天津市捷威动力工业有限公司 A kind of lithium ion battery of high dispersive mends lithium material and preparation method thereof
CN109546100A (en) * 2018-10-16 2019-03-29 中航锂电（洛阳）有限公司 A kind of silicon-carbon composite film electrode and lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YONG SEOK KIM，ET AL.: "The critical contribution of unzipped graphene nanoribbons to scalable silicon-carbon fiber anodes in rechargeable Li-ion batteries" *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021179219A1 (en) * 2020-03-11 2021-09-16 宁德新能源科技有限公司 Anode plate and manufacturing method therefor, battery using anode plate, and electronic apparatus
CN115088101A (en) * 2020-03-11 2022-09-20 宁德新能源科技有限公司 Anode pole piece and preparation method thereof, battery adopting anode pole piece and electronic device
JP2023515589A (en) * 2020-03-11 2023-04-13 寧徳新能源科技有限公司 Anode piece and its preparation method, battery and electronic device using said electrode piece
JP7465362B2 (en) 2020-03-11 2024-04-10 寧徳新能源科技有限公司 Anode piece and its preparation method, battery and electronic device using said anode piece
CN113422009A (en) * 2021-06-01 2021-09-21 广东工业大学 Lithium ion battery cathode material and preparation method and application thereof
CN113422009B (en) * 2021-06-01 2022-03-18 广东工业大学 Lithium ion battery cathode material and preparation method and application thereof
CN116169255A (en) * 2021-11-25 2023-05-26 湖南中科星城石墨有限公司 Silicon-carbon negative electrode material of lithium ion battery, and preparation method and application thereof
WO2024050756A1 (en) * 2022-09-08 2024-03-14 宁德时代新能源科技股份有限公司 Silicon-carbon negative electrode material and preparation method therefor, secondary battery and electric device

Also Published As

Publication number Publication date
CN110729460B (en) 2023-06-30

Similar Documents

Publication Publication Date Title
CN110729460B (en) Nano silicon composite lithium supplementing negative electrode material of lithium ion battery and preparation method and application thereof
CN103474632B (en) A kind of negative material for lithium battery and its preparation method and application
CN110729467A (en) Lithium ion battery carbon nanotube composite lithium-supplementing negative plate and preparation method thereof
CN110224182B (en) Method for pre-lithiation of lithium ion battery
CN110729468A (en) Lithium ion battery carbon nanotube composite lithium supplement material and preparation method and application thereof
CN110518226B (en) Silicon-carbon composite negative electrode material and preparation method thereof
CN110729459A (en) Lithium ion battery cathode composite lithium supplement material and preparation method thereof
CN110581310B (en) Method for inhibiting growth of lithium dendrite by coating organic compound
CN112397706A (en) Lithium ion battery cathode material structure, preparation method thereof and lithium ion battery
CN109286014A (en) A kind of Si-C composite material and its preparation method and application that surface is modified
CN108923037A (en) A kind of Silicon-rich SiOx-C material and its preparation method and application
CN109473665A (en) A kind of nano silica-base material and its preparation method and application
CN110729452A (en) Lithium ion battery negative pole piece and preparation method thereof
CN111180712B (en) Nano silicon/carbon nano tube microsphere/graphite composite structure negative electrode material and preparation method thereof
CN109942001B (en) Silicon negative electrode material with spherical thorn-shaped structure and preparation method thereof
Fu et al. High reversible silicon/graphene nanocomposite anode for lithium-ion batteries
CN110240145A (en) A kind of Metal Substrate array carbon nano tube electrode material and its preparation method and application of no transition zone support
CN110474037B (en) Preparation method of porous silicon-carbon composite negative electrode material
CN105047894A (en) Preparation method of halogen-doped carbon and silicon nano-material and application thereof
Wang et al. Improved performance for lithium-ion batteries with nickel nanocone-arrays supported germanium anode
CN114203994B (en) Preparation method and application of positive electrode material of lithium-sulfur battery
CN116230933A (en) Method for removing alkali from surface of pre-lithiated anode material
CN114824168A (en) Lithium supplement agent and method for lithium ion battery anode, anode plate, lithium supplement slurry and battery
CN109860527B (en) Carbon-based composite material for preparing lithium battery cathode and preparation method thereof
Lee et al. Synthesis and Electrochemical Performance of Transition Metal-Coated Carbon Nanofibers on Ni Foam as Anode Materials for Lithium Secondary Batteries

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