CN110729460B - 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
CN110729460B
CN110729460B CN201910941095.XA CN201910941095A CN110729460B CN 110729460 B CN110729460 B CN 110729460B CN 201910941095 A CN201910941095 A CN 201910941095A CN 110729460 B CN110729460 B CN 110729460B
Authority
CN
China
Prior art keywords
lithium
ion battery
lithium ion
nano
graphene
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
CN201910941095.XA
Other languages
Chinese (zh)
Other versions
CN110729460A (en
Inventor
张立君
陈慧龙
段恒志
王建军
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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a nano-silicon composite lithium-supplementing negative electrode material of a lithium ion battery, a preparation method and application thereof. The composite lithium-supplementing negative electrode material is prepared by adopting a chemical deposition method and electrostatic spinning, and the obtained lithium ion battery composite lithium-supplementing negative electrode material has stable performance and high safety, can realize uniform lithium supplementation, improves the first efficiency and energy density of the lithium ion battery, effectively improves the conductivity of the lithium ion battery, and ensures the long cycle and excellent rate capability of the lithium ion battery. The preparation method of the composite lithium-supplementing negative electrode 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 supplementing negative electrode material for 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 a focus of development competition of the automobile industry. With the continuous development of lithium ion batteries in the fields of portable electronic equipment, electric bicycles and electric automobiles, the requirements on the performances such as energy density and the like of the lithium ion batteries are higher and higher.
The traditional commercial lithium ion battery mainly adopts graphite carbon materials as the negative electrode materials, however, the theoretical specific capacity of the commercial graphite negative electrode materials is only 372mAh/g, and silicon is far higher than the theoretical specific capacity of commercial graphite because the theoretical specific capacity of the commercial graphite negative electrode materials is up to 4200mAh/g, and the commercial lithium ion battery is wide in source, low in cost and environment-friendly, so that the commercial lithium ion battery is always concerned by researchers, and is one of the negative electrode materials of the next generation lithium ion battery with the highest potential. However, silicon has serious volume expansion (300-400%) in the charge-discharge process, so that the silicon bears great mechanical force in charge-discharge cycle and gradually pulverizes and collapses, the connection between active materials and current collectors is affected, and the electron transmission is not facilitated; on the other hand, the solid electrolyte interface film formed between the silicon-based material and the electrolyte is gradually thickened, which is unfavorable for improving the capacity of the lithium battery and causes the cycle performance of the lithium battery to be drastically reduced. Therefore, developing a high-capacity and long-cycle-life lithium ion battery anode material is a technical problem which is urgently needed to be solved in the industry at present.
In addition, in the first charge and discharge process of the lithium ion battery, the electrode material reacts with the electrolyte at the solid-liquid phase interface to form a solid electrolyte film (SEI film) passivation film, and a large amount of active lithium ions are consumed, so that the first irreversible coulomb 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 supplementing modes comprise an in-situ doping lithium supplementing method, an electrochemical lithium supplementing method and a chemical pre-lithium supplementing method, however, the methods have high environmental requirements and potential safety hazards such as inflammability, and the further popularization and application of each method are limited.
CN103346325B discloses a lithium ion battery anode material, which comprises graphene, nano silicon particles distributed in a graphene lamellar structure and a netlike carbon material distributed between the graphene lamellar structure and the nano silicon particles. In the lithium ion battery anode material provided by the invention, the graphene sheet layer and the carbon material with the network structure are tightly contacted with the nano silicon particles, so that the conductivity of the nano silicon particles is improved; meanwhile, in the charge and discharge process, huge volume change of silicon particles can be effectively buffered, so that the lithium ion battery anode material provided by the invention has better cycle performance. However, the material does not contain lithium ions, so that the material cannot play a role in lithium supplementation although the material has a higher capacity remaining rate after circulation.
CN109301188A discloses a lithium ion battery lithium supplementing material with high dispersion, which is a graphene sheet with uniformly dispersed metal lithium particles on the surface; the surface of the metal lithium particles is coated with a carbon layer; the lithium ion battery lithium supplementing material can obviously improve the first charge and 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 dead lithium is caused, and the effectiveness of the material is greatly reduced.
Disclosure of Invention
The invention aims at solving the problems and provides a preparation method of a nano silicon composite lithium supplementing negative electrode material of a lithium ion battery, which develops the nano silicon composite lithium supplementing negative electrode material of the lithium ion battery with good dispersion of metal lithium and nano silicon and excellent electrochemical performance.
In one aspect, the invention provides a nano-silicon composite lithium-supplementing negative electrode material of a lithium ion battery, 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 a 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 metal lithium particles is as follows: 1:0.1 to 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 supplementing anode material, which comprises the following steps:
(1) Under the protection of inert gas, using silane gas to chemically vapor deposit nano silicon particles on graphene;
(2) Adding the material obtained in the step (1) and the 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 material;
(4) And (3) taking alkane gas as a carbon source, and calcining at a high temperature to carry out carbon coating on the spinning material obtained in the step (3) to obtain the nano-silicon composite lithium supplementing anode 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 specific operation of the thermal chemical vapor deposition is as follows: introducing silane gas into a furnace with graphene, heating to thermally decompose the silane gas, and depositing nano silicon particles on the surface of the graphene;
the flow rate of the silane gas is 1.0-2.0L/min, and the introducing time is 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, tertiary 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: adding the material obtained in the step (1) and the organic lithium solution into an alkane solvent under inert atmosphere, and sequentially performing ultrasonic dispersion and magnetic stirring;
the inert atmosphere is one or a combination of nitrogen and argon;
the ultrasonic dispersion time is 90-180 min, the magnetic stirring temperature is 40-80 ℃ and the ultrasonic dispersion time is 12-24 h.
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 spinneret used for the electrostatic spinning is 0.6-1.6 mm.
In the step (4), the temperature rising 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 supplementing negative electrode material comprises the following steps:
(1) Placing 10g of graphene in a tube 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 cause the monosilane gas to be thermally decomposed, introducing for 30min, and depositing on the surface of the graphene to generate nano silicon particles;
(2) Then adding the material obtained in the step (1) and 100mL of 1mol/L butyl lithium into 30mL of cyclohexane solution, performing ultrasonic dispersion for 2h, and magnetically stirring at 40 ℃ for 24h to obtain a dispersion liquid;
(3) Filling the dispersion liquid obtained in the step (2) into a disposable injector, placing the disposable injector into an electrostatic spinning instrument, carrying out electrostatic spinning by adopting a spinneret with the diameter of 1.0mm, carrying out electrostatic spinning at the voltage of 20KV and the spraying speed of 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning liquid, and drying to obtain a spinning product;
(4) And (3) taking off the spinning material obtained in the step (3), placing the spinning material in a muffle furnace, heating the muffle furnace to 700 ℃ at a speed of 5 ℃/min, and carrying out carbon coating for 3 hours by taking methane gas as a carbon source to obtain the material, namely the nano-silicon composite lithium-supplementing anode material of the lithium ion battery.
On the other hand, the invention also provides the application of the composite lithium-supplementing anode material or the method in the preparation of lithium ion batteries.
The beneficial effects of the invention are as follows:
(1) According to the composite lithium supplementing negative electrode material, fibrous graphene is used as a carrier, nano silicon particles and metal lithium particles are distributed in the graphene and on the surface of the graphene, and as part of nano silicon and metal lithium particles are distributed in the graphene, the problem that silicon simple substances directly contact electrolyte to react violently in the circulation of a lithium ion battery is effectively solved, the phenomenon that carbon on the surface is separated from the surface of the graphene in the circulation process of the battery to cause dead lithium is avoided, and lithium supplementation 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 of the graphene and the nano silicon particles, and the long-cycle performance of the lithium ion battery is improved.
(2) According to the invention, the composite lithium-supplementing negative electrode material is prepared by adopting a chemical deposition method and electrostatic spinning, so that the lithium-supplementing negative electrode material distributed with nano silicon particles and metal lithium particles is obtained, and the lithium-supplementing negative electrode material of the lithium ion battery has stable performance and high safety, can realize uniform lithium supplementation, improves the first efficiency and energy density of the lithium ion battery, effectively improves the conductivity of the lithium ion battery, and ensures the long cycle and excellent rate capability of the lithium ion battery.
(4) The preparation method of the composite lithium-supplementing negative electrode material is simple and easy to realize.
Drawings
Fig. 1 is a schematic view of a part of a scanning electron microscope of a composite lithium-compensating negative electrode material prepared in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the general concepts 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. However, it will be apparent to one skilled in the art that the present application may be practiced without one or more of these details. In other instances, some features well known in the art have not been described in order to avoid obscuring the present application.
Unless otherwise indicated, the starting materials in the examples below are all commercially available.
Example 1
A nano silicon composite lithium supplementing negative electrode material of a lithium ion battery comprises the following components: the graphene comprises fibrous graphene, nano silicon particles deposited inside 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 nano silicon composite lithium supplementing negative electrode material of the lithium ion battery 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 cause the monosilane gas to be thermally decomposed, introducing for 30min, and depositing on the surface of the graphene to generate nano silicon particles;
(2) Then adding the material obtained in the step (1) and 100mL of 1mol/L butyl lithium into 30mL of cyclohexane solution, performing ultrasonic dispersion for 2h, and magnetically stirring at 40 ℃ for 24h to obtain a dispersion liquid;
(3) Filling the dispersion liquid obtained in the step (2) into a disposable injector, placing the disposable injector into an electrostatic spinning instrument, carrying out electrostatic spinning by adopting a spinneret with the diameter of 1.0mm, carrying out electrostatic spinning at the voltage of 20KV and the spraying speed of 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning liquid, and drying to obtain a spinning product;
(4) And (3) taking off the spinning material obtained in the step (3), placing the spinning material in a muffle furnace, heating the muffle furnace to 700 ℃ at a speed of 5 ℃/min, and carrying out carbon coating for 3 hours by taking methane gas as a carbon source to obtain the material, namely the nano-silicon composite lithium-supplementing anode material of the lithium ion battery.
Comparative example 1
Comparative example 1 provides a graphene sheet having metallic lithium particles dispersed on the surface, prepared by the following method:
(1) Adding 1ml of n-butyllithium solution and 1mg of graphene sheets into 30ml of ethylene oxide solution under a nitrogen environment, then placing the mixture into a high-pressure reaction kettle, and screwing the reaction kettle; (2) The high-pressure reaction kettle is placed in an oil bath at 110 ℃ for reaction for 20 hours; (3) Washing the reacted product with tetrahydrofuran solution for 3 times, and vacuum drying; (4) Placing the cleaned product in a muffle furnace at 700 ℃, and carrying out carbon coating for 3 hours by taking methane gas as a carbon source to obtain a material, namely the high-dispersion flaky lithium ion battery lithium supplementing material.
Test examples
Electrochemical performance test: and (3) spraying the composite lithium-supplementing negative electrode material prepared in the embodiment 1 on a copper foil current collector to prepare a lithium ion battery negative electrode plate, and respectively obtaining the lithium ion batteries with the numbers A-D. And adding the lithium supplementing material prepared in the comparative example 1 into a silicon-based negative electrode material, uniformly mixing, spraying the mixture onto a copper foil current collector, and preparing a lithium ion battery negative electrode plate to obtain the lithium ion battery with the number of E. And the first charge and discharge efficiency, the capacity remaining rate after 100 weeks of cycle, and the battery energy density of each example lithium ion battery were measured, wherein the battery data are all average values of at least 5 parallel battery test results, and the obtained results are shown in table 1.
The method for testing the coulombic efficiency of the first charge and discharge refers to the national standard GB/T24533-2009 lithium ion battery graphite cathode material; the cycle performance test method is as follows: charging the battery to an upper limit voltage at 23 ℃ with 0.5C constant current, then converting to constant voltage charging, and stopping current at 0.05C; standing for 10min, discharging to 2.7V at 0.5C constant current, and measuring to obtain initial discharge capacity C of the battery 0 The method comprises the steps of carrying out a first treatment on the surface of the After 10min of standing, repeating the above stepsStep 100 weeks, performing continuous charge and discharge test to obtain capacity C of the battery after 100 times of circulation 1 . The remaining capacity of the battery after 100 cycles was calculated as follows: capacity remaining ratio=c 1 /C 0 X 100%. The battery energy density measurement method is as follows: charging the current to the upper limit voltage at the temperature of 23 ℃ with a constant current of 0.5 ℃, then converting to constant voltage charging, and stopping the current at 0.05 ℃; standing for 10min, discharging to 2.7V at 0.5C constant current, and measuring to obtain the discharge capacity of the battery; after 10min of rest, the above steps were repeated 3 times, and the average value of the discharge capacity of 3 times was calculated. The different types of batteries were weighed using an electronic balance. The 23 ℃ cell energy density was calculated according to the following formula: battery energy density = discharge average capacity x median voltage/battery weight. The internal resistance measurement was performed on the battery after 100 weeks of cycling using an ac impedance meter. And adopting a Land battery test system to perform constant current charge and discharge test on the assembled analog battery. 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-supplementing negative electrode material provided in example 1 can effectively improve the first charge-discharge efficiency and cycle performance of the battery, and especially the battery capacity retention rate after 100 weeks of cycle can be up to 99%. While in the battery of the lithium-supplementing anode material provided in comparative example 1, the improvement effect is not as good as that of example 1, although the coulombic efficiency of the first charge and discharge and the capacity remaining rate after 100 cycles are improved, in addition, the energy density, the first reversible capacity and the discharge capacity of example 1 are significantly higher than those of comparative example 1, and the internal resistance of the battery of example 1 is significantly lower than that of comparative example 1, which means that the composite lithium-supplementing anode material provided in the invention can significantly improve the conductivity of the battery active material.
Example 2
A nano silicon composite lithium supplementing negative electrode material of a lithium ion battery comprises the following components: the graphene comprises fibrous graphene, nano silicon particles deposited inside 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 nano silicon composite lithium supplementing negative electrode material of the lithium ion battery comprises the following steps:
(1) 10g of graphene is placed in a tube furnace, trichlorosilane gas is introduced into the furnace at a low flow rate of 1.0L/min under the protection of nitrogen, and is heated to 750 ℃ to cause thermal decomposition of the trichlorosilane gas, the introduction time is 30min, and nano silicon particles are deposited on the surface of the graphene;
(2) Adding the material obtained in the step (1) and 100mL of tert-butyllithium with the concentration of 1mol/L into 30mL of cyclohexane solution, performing ultrasonic dispersion for 2h, magnetically stirring at 40 ℃ for 24h, and uniformly mixing to obtain a dispersion liquid;
(3) Filling the dispersion liquid obtained in the step (2) into a disposable injector, placing the disposable injector into an electrostatic spinning instrument, carrying out electrostatic spinning by adopting a spinneret with the diameter of 0.6mm, carrying out electrostatic spinning at the voltage of 20KV and the spraying speed of 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning liquid, and drying to obtain a spinning product;
(4) And (3) taking off the spinning material obtained in the step (3), placing the spinning material in a muffle furnace, heating the muffle furnace to 700 ℃ at a speed of 5 ℃/min, and carrying out carbon coating for 3 hours by taking methane gas as a carbon source to obtain the material, namely the nano-silicon composite lithium-supplementing anode material of the lithium ion battery.
Example 3
A nano silicon composite lithium supplementing negative electrode material of a lithium ion battery comprises the following components: the graphene comprises fibrous graphene, nano silicon particles deposited inside 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 nano silicon composite lithium supplementing negative electrode material of the lithium ion battery comprises the following steps:
(1) Placing 10g of graphene in a tube 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 cause the dichlorosilane gas to be thermally decomposed, introducing for 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 phenyl lithium with the concentration of 1mol/L into 30mL of cyclohexane solution in a nitrogen environment, performing ultrasonic dispersion for 2h, magnetically stirring at 40 ℃ for 24h, and uniformly mixing to obtain a dispersion liquid;
(3) Filling the spinning solution obtained in the step (2) into a disposable injector, placing the disposable injector into an electrostatic spinning instrument, carrying out electrostatic spinning by adopting a spinneret with the diameter of 1.6mm, carrying out electrostatic spinning at the voltage of 20KV and the spraying speed of 0.02mm/s, winding a circle of aluminum foil on a receiving roller, receiving the sprayed spinning solution, and drying to obtain a spinning product;
(4) And (3) taking off the spinning material obtained in the step (3), placing the spinning material in a muffle furnace, heating the muffle furnace to 700 ℃ at a speed of 5 ℃/min, and carrying out carbon coating for 3 hours by taking methane gas as a carbon source to obtain the material, namely the nano-silicon composite lithium-supplementing anode material of the lithium ion battery.
The foregoing is merely exemplary of the present application, and the scope of the present application is not limited to the specific embodiments, but is defined by the claims of the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.

Claims (16)

1. A nano silicon composite lithium supplementing negative electrode material of a lithium ion battery is characterized in that: the composite lithium supplementing negative electrode material comprises fibrous graphene obtained through electrostatic spinning treatment, nano silicon particles deposited in the graphene and on the surface of the graphene, and metal lithium particles distributed in the graphene and on the surface of the graphene, wherein at least a part of the surface of the graphene is coated with a carbon layer; the mass ratio of the graphene to the nano silicon particles to the metal lithium particles is 1:0.1 to 5:0.01 to 0.3.
2. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material as claimed in claim 1, which is characterized in that: the method comprises the following steps:
(1) Under the protection of inert gas, using silane gas to chemically vapor deposit nano silicon particles on graphene;
(2) Adding the material obtained in the step (1) and the 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 material;
(4) And (3) taking alkane gas as a carbon source, and calcining at a high temperature to carry out carbon coating on the spinning material obtained in the step (3) to obtain the nano-silicon composite lithium supplementing anode material of the lithium ion battery.
3. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material according to claim 2, which is characterized in that: in the step (1), the inert gas is one or a combination of nitrogen and argon.
4. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material according to claim 2, which is characterized in that: the silane gas is any one of monosilane, trichlorosilane and dichlorosilane.
5. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material according to claim 2, which is characterized in that: the chemical vapor deposition is thermal chemical vapor deposition.
6. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material is characterized by comprising the following steps of: the specific operation of the thermal chemical vapor deposition is as follows: and introducing silane gas into a furnace with graphene, heating to thermally decompose the silane gas, and depositing nano silicon particles on the surface of the graphene.
7. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material, which is characterized in that: the flow rate of the silane gas is 1.0-2.0L/min, and the introducing time is 30-60 min; the heating temperature is 700-1000 ℃.
8. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material according to claim 2, which is characterized in that: in the step (2), the alkane solvent is an n-ethane solution or a cyclohexane solution.
9. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material according to claim 2, which is characterized in that: the organic lithium solution is one or a mixture of more than two of butyl lithium, tertiary butyl lithium or phenyl lithium.
10. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material, which is characterized in that: the concentration of the organic lithium solution is 0.1-5 mol/L.
11. The method for preparing the nano-silicon composite lithium-supplementing anode material of the lithium ion battery according to any one of claims 2 to 10, which is characterized by comprising the following steps: the specific operation of the step (2) is as follows: and (3) adding the material obtained in the step (1) and the organic lithium solution into an alkane solvent under inert atmosphere, and sequentially performing ultrasonic dispersion and magnetic stirring.
12. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material, which is characterized in that: the inert atmosphere is one or a combination of nitrogen and argon.
13. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material, which is characterized in that: the ultrasonic dispersion time is 90-180 min, the magnetic stirring temperature is 40-80 ℃ and the ultrasonic dispersion time is 12-24 h.
14. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material according to claim 2, which is characterized in that: 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 spinneret used for the electrostatic spinning is 0.6-1.6 mm.
15. The method for preparing the lithium ion battery nano-silicon composite lithium supplementing anode material according to claim 2, which is characterized in that: in the step (4), the temperature rising rate of the high-temperature calcination is 1-5 ℃/min, the calcination temperature is 600-900 ℃ and the calcination time is 2-4 h.
16. Use of the composite lithium-compensating negative electrode material of claim 1 or the method of any of claims 2 to 15 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 CN110729460A (en) 2020-01-24
CN110729460B true 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)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2022193286A1 (en) * 2021-03-19 2022-09-22 宁德新能源科技有限公司 Negative electrode material and preparation method therefor, electrochemical device and electronic device
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
CN116169255B (en) * 2021-11-25 2024-06-14 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 (5)

* 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
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
WO2017083804A1 (en) * 2015-11-13 2017-05-18 SiNode Systems, Inc. Graphene-encapsulated electroactive material for use in a lithium ion electrochemical cell
KR20180039984A (en) * 2016-10-11 2018-04-19 재단법인대구경북과학기술원 Silicon-graphene composites, method for preparing the same and lithium ion battery comprising the same
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

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102100352B1 (en) * 2011-08-29 2020-04-13 가부시키가이샤 한도오따이 에네루기 켄큐쇼 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
US10553871B2 (en) * 2012-05-04 2020-02-04 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
CN103346325B (en) * 2013-06-28 2015-12-23 中国科学院宁波材料技术与工程研究所 A kind of lithium ion battery negative material, its 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
CN105552316B (en) * 2014-10-27 2018-09-18 财团法人工业技术研究院 Negative electrode material for lithium ion battery and lithium ion battery comprising 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
EP3400624B1 (en) * 2016-01-04 2020-11-18 Airbus Singapore Private Limited Graphene anode comprising a group iv-vi compound and a catalyst
CN105914343B (en) * 2016-07-11 2018-11-30 洛阳力容新能源科技有限公司 Anode plate for lithium ionic cell, preparation method and application, 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
CN107768659A (en) * 2016-08-15 2018-03-06 福建新峰二维材料科技有限公司 A kind of preparation method of the sulfur electrode material of loose structure
CN107768607B (en) * 2016-08-15 2020-10-16 福建新峰二维材料科技有限公司 Preparation method of lithium ion battery negative electrode material
CN107768608B (en) * 2016-08-15 2020-10-16 福建新峰二维材料科技有限公司 Preparation method of lithium ion battery cathode material capable of effectively buffering silicon volume effect
CN106876689B (en) * 2017-03-24 2020-02-21 中航锂电（洛阳）有限公司 Nitrogen-doped graphene-silicon composite negative electrode material, preparation method thereof and 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
CN107492645B (en) * 2017-08-09 2020-06-26 深圳市金牌新能源科技有限责任公司 Silicon oxide-graphene composite material and preparation method thereof
CN107611391A (en) * 2017-09-05 2018-01-19 珠海格力电器股份有限公司 Lithium metal secondary battery cathode and preparation method thereof
CN108511758B (en) * 2018-03-23 2020-08-18 安普瑞斯（无锡）有限公司 Negative electrode aqueous lithium supplement additive and preparation method thereof
CN109301188B (en) * 2018-09-11 2021-08-03 天津市捷威动力工业有限公司 High-dispersion lithium ion battery lithium supplement material and preparation method thereof

Patent Citations (5)

* 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
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
WO2017083804A1 (en) * 2015-11-13 2017-05-18 SiNode Systems, Inc. Graphene-encapsulated electroactive material for use in a lithium ion electrochemical cell
KR20180039984A (en) * 2016-10-11 2018-04-19 재단법인대구경북과학기술원 Silicon-graphene composites, method for preparing the same and lithium ion battery comprising the same
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

Also Published As

Publication number Publication date
CN110729460A (en) 2020-01-24

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
CN108493421B (en) Preparation method of tin-silicon-based graphene ball cathode material for lithium ion battery
CN108649190A (en) Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application
CN110224182B (en) Method for pre-lithiation of lithium ion battery
CN110729467A (en) Lithium ion battery carbon nanotube composite lithium-supplementing negative plate and preparation method thereof
CN110729468A (en) Lithium ion battery carbon nanotube composite lithium supplement material and preparation method and application 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
CN115663157B (en) Hard carbon composite material for lithium ion battery and preparation method thereof
CN111180712B (en) Nano silicon/carbon nano tube microsphere/graphite composite structure negative electrode material and preparation method thereof
CN115692677A (en) High-power low-expansion silica metal oxide composite material and preparation method thereof
CN115566167A (en) Silicon-based composite material prepared by gaseous atomization method and preparation method
CN110729452A (en) Lithium ion battery negative pole piece 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
CN112289985B (en) C @ MgAl2O4Composite coating modified silicon-based negative electrode material and preparation method thereof
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
CN116404124A (en) Hard carbon composite material for lithium ion battery and preparation method thereof
CN116230933A (en) Method for removing alkali from surface of pre-lithiated anode material
CN112909228B (en) Modified negative pole piece and preparation method and application thereof
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
CN116154141B (en) Silicon-carbon negative electrode material with watermelon-like structure and preparation method thereof

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