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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

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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
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lithium
ion battery
lithium ion
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graphene
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张立君
陈慧龙
段恒志
王建军
曹雁超
王念贵
王瑛
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Shandong Yuhuang New Energy Technology Co Ltd
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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.
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