CN111653738B - Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof - Google Patents

Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof Download PDF

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CN111653738B
CN111653738B CN202010313114.7A CN202010313114A CN111653738B CN 111653738 B CN111653738 B CN 111653738B CN 202010313114 A CN202010313114 A CN 202010313114A CN 111653738 B CN111653738 B CN 111653738B
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lithium ion
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CN111653738A (en
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张小祝
苏敏
单沈桃
李慧
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Wanxiang A123 Systems Asia Co Ltd
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    • 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
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    • 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
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    • 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
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Abstract

The invention relates to the technical field of lithium ion batteries, and provides a silicon-carbon negative electrode material of a lithium ion battery and a preparation method thereof, aiming at solving the problems that the existing silicon-based negative electrode material of the lithium ion battery is easy to expand in volume in the charging and discharging processes, so that the battery circulation and the rate capability are poor; the shell of the lithium ion battery silicon-carbon negative electrode material is an amorphous carbon layer. According to the invention, the volume stress is relieved through material nanocrystallization, the volume expansion of the silicon-based material is relieved by combining the compounding of the conductive agent and the carbon coating, the use of a graphite matrix material is avoided, and the size of the material is more controllable; the outer amorphous carbon layer that is through carbon layer structure disorder, promotes the multiplying power and the cycling performance of material, can not reduce combined material's first effect simultaneously, and the comprehensive properties is better.

Description

Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-carbon negative electrode material of a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries are widely applied in the fields of portable electronic devices, electric automobiles and the like due to the advantages of high energy density, long cycle life and the like, the current commercialized lithium ion battery cathode materials are mainly graphite carbon materials, but with the continuous improvement of market demands, the research and development of the graphite materials are close to the limit, but the essential defect of low theoretical capacity (372mAh/g) cannot be overcome, so that the development of cathode materials with higher energy density is urgent.
The silicon-based negative electrode material is a next-generation negative electrode material which is hopeful to replace graphite due to the advantages of high energy density, good safety performance, wide resources and the like, the research on the silicon-based negative electrode material is generally divided into two directions, one is a route of nano-silicon, the route mainly realizes the improvement of the cycle performance through the design of a silicon-carbon material structure, such as a structure of dispersing nano-silicon on the surface of spherical graphite, a structure of embedding graphite particles in lamellar graphite and the like, and researchers design structures of pomegranate type, watermelon type, dragon fruit type and the like, although the novel silicon-carbon structures can improve the cycle performance to a certain degree, the preparation process is relatively complex, the cost is higher, and the problems of agglomeration of nano-silicon and pulverization at the later cycle stage still exist; the other route is a route of the silicon oxide, the route directly carries out carbon coating on the silicon oxide material by a solid phase method, a liquid phase method or a gas phase method, and combines means such as metal reduction, pre-lithiation and the like to solve the problems of the first effect and the like of the silicon oxide material.
Chinese patent literature discloses 'a silicon-carbon composite material, a lithium ion battery and a preparation method and application thereof', and application publication No. CN 103633295A, silicon powder and silica powder are mixed and then added into a solution containing a binder and a dispersing agent, ball milling is carried out to obtain nano slurry, graphite and a conductive agent are continuously added into the nano slurry, spray drying is carried out to obtain spherical particles, the spherical particles are mixed with asphalt and then are subjected to coating treatment and carbonization to obtain a finished silicon-carbon material, matrix graphite with larger particle size is added in the granulation process, a certain proportion of the binder is added, the particle size is increased due to the bonding between the graphite and the graphite, the initial discharge capacity of the prepared material is 640mAh/g, the initial efficiency is 80%, and the performance is not good.
The invention discloses a preparation method of a silicon-silicon oxide-carbon composite cathode material of a lithium ion battery, and the application publication number is CN 103730644A, in the protection of argon atmosphere, silicon oxide, silicon and graphite are subjected to mechanical ball milling and mixing to obtain a primary mixed material, then the primary mixed material is uniformly mixed with asphalt and an organic solvent, and the primary mixed material is dried and calcined to obtain the silicon-carbon composite material.
In order to improve the performance of a silicon-based negative electrode material to meet the increasing market demand, a great deal of research is carried out, and remarkable results are obtained, in the existing technical scheme, a nano silicon route and a silicon oxide route are relatively independent and are advanced to a certain extent, some researchers combine nano silicon and a silicon oxide material, the performance of the whole material is improved by taking the advantages of the nano silicon and/or the silicon oxide and graphite into consideration, and the graphite is used as a matrix, and the nano silicon and/or the silicon oxide and the graphite are attached to the graphite matrix to prepare a silicon-carbon material, so that the problem that the size of the final material is large and the cycle effect is influenced due to the combination of the graphite and the graphite cannot be avoided.
In addition, the existing silicon-carbon coating mode basically heats the coating agents such as soft carbon, hard carbon and the like directly under an inert condition, so that the cracking and carbonization of a carbon source achieve the coating effect, and the performance of a coating layer cannot be well exerted due to the lack of pretreatment of a coating material.
Disclosure of Invention
The invention provides a silicon-carbon cathode material of a lithium ion battery, which has high structural stability and controllable size, can relieve volume stress and effectively improve the first efficiency of the battery, and aims to solve the problem that the conventional silicon-carbon cathode material of the lithium ion battery is easy to expand in volume in the charging and discharging processes, so that the battery is poor in cycle and rate performance.
The invention also provides a preparation method of the silicon-carbon cathode material of the lithium ion battery, which is simple to operate, low in cost and free of pollution, in order to overcome the problems that the existing preparation process of the silicon-based cathode material of the lithium ion battery is relatively complex, high in cost and mostly adopts toxic reagents.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery silicon-carbon negative electrode material is of a core-shell structure, and the inner core of the lithium ion battery silicon-carbon negative electrode material is secondary particles formed by crosslinking nano silicon and nano silicon monoxide through a conductive agent; the shell of the lithium ion battery silicon-carbon negative electrode material is an amorphous carbon layer.
The silicon-carbon cathode material of the lithium ion battery is of a core-shell structure as a whole, the inner core of the silicon-carbon cathode material is secondary particles formed by crosslinking nano silicon and nano silicon oxide through a conductive agent, the volume stress is relieved through material nanocrystallization, the respective advantages of the nano silicon and the silicon oxide are combined, the conductive agent playing a crosslinking role can relieve the volume expansion of a silicon-based material while the conductivity of the material is enhanced, in addition, the use of a base material is avoided, and the size of the material is more controllable; the outer layer is an amorphous carbon layer which is an asphalt-based carbon source and shows hard carbon characteristics after being subjected to peroxidation and carbonization, the multiplying power and the cycle performance of the material are improved through carbon layer structure disorder, and compared with pure hard carbon coating, the composite material has the advantages that the first effect of the composite material cannot be reduced, so that the prepared silicon-carbon material has better comprehensive performance.
Preferably, the conductive agent is carbon nanotubes, graphene or carbon nanofibers; the conductive agent is in a linear, tubular, sheet or net structure.
Preferably, the particle size of the nano silicon and the nano silicon monoxide is 80-120 nm; the mass ratio of the nano silicon to the nano silicon monoxide is 1: (6-10).
The size of the nano silicon and the nano silicon oxide is the better size which can be processed by the sand mill, the equipment can stably run and the material meeting the requirement can be prepared; the mass ratio of the nano silicon to the nano silicon oxide is controlled within a certain range, so that the uniform dispersion of the nano silicon and the nano silicon oxide and the controllable structure of a finished product are ensured, the agglomeration phenomenon is very serious when the ratio of the nano silicon is too high, and the reversible capacity and the first effect of the finished product are lower when the ratio of the nano silicon oxide is too high.
Preferably, the mass ratio of the conductive agent to the nano silicon is 1: (1-8).
Preferably, the ratio of the amorphous carbon layer to the total mass of the nano silicon and the nano silicon monoxide is 1: (5-20), the ratio of which is greatly different according to the residual carbon value of the carbon source.
Preferably, the particle size D50 of the silicon-carbon negative electrode material of the lithium ion battery is 1-20 μm.
A preparation method of a silicon-carbon negative electrode material of a lithium ion battery comprises the following steps:
(1) adding a dispersing agent and deionized water into nano silicon and nano silicon monoxide, and sanding to obtain slurry; the nano silicon and the nano silicon oxide are obtained by adding micron-sized silicon powder and micron-sized sub-silicon oxide powder into deionized water, adding a dispersing agent and sanding to reach a nano size. Adding micron-sized silicon powder, micron-sized sub-silicon oxide powder and a dispersing agent in a certain proportion into a stirring tank, stirring for a certain time, transferring the slurry into a sand mill through a diaphragm pump, forming a circulating system between the stirring tank and the sand mill through the diaphragm pump so as to add materials into the slurry through the stirring tank at any time, loading nanoscale zirconia balls into the sand mill, sampling and testing the granularity of the slurry after sanding at intervals of a certain time, and stopping sanding when the granularity D50 of the slurry is less than 100 nm; the size of the micron-sized silicon powder is 5-50 microns, preferably 10-20 microns, the size of the micron-sized sub-silicon oxide powder is 1-50 microns, preferably 10-20 microns, the mass ratio of the micron-sized silicon powder to the micron-sized sub-silicon oxide powder is 1 (6-10), preferably 1 (8-9), and the size of the mixed slurry after sanding is 80-120 nm;
(2) adding a conductive agent solution into the slurry, uniformly stirring, and performing spray drying to obtain secondary particle powder;
(3) and adding a carbon source into the secondary particle powder, kneading, and performing heat treatment to obtain the silicon-carbon cathode material of the lithium ion battery. The kneading step is to combine the three components of nano-silicon Si-conductive agent-silicon monoxide more tightly into secondary particles and to disperse the carbon source on the surface of the secondary particles better, so as to achieve the best coating effect.
Preferably, in the step (1),
the dispersing agent is one or more of polyvinylpyrrolidone (PVP), Polyethylene (PE), polypropylene (PP), Polystyrene (PS) and Cetyl Trimethyl Ammonium Bromide (CTAB);
the mass ratio of the dispersing agent to the nano silicon is 1: (1.5-4);
the mass ratio of the conductive agent to the nano silicon is 1: (1-8);
the ratio of the deionized water to the total mass of the nano silicon and the nano silicon monoxide is (4-10): 1.
preferably, in the step (2), the spray drying is carried out by using a spray dryer; the spray dryer is a closed circulation system, and the circulating gas is N2(ii) a The inlet temperature of the spray dryer is 200-240 ℃, and the outlet temperature of the spray dryer is 250-340 Hz; the particle size D50 of the secondary particle powder is controlled to be 3-20 mu m.
Preferably, in the step (3), the carbon source is one or more of coal-series pitch, petroleum-series pitch and a mixture of coal-series pitch and petroleum-series pitch and a resin carbon material.
Preferably, in the step (3), the heat treatment is divided into two stages, wherein the first stage adopts oxygen, air or a mixed atmosphere of oxygen and inert gas; the heat treatment temperature of the first stage is 200-400 ℃, and the heat treatment time is 1-6 h; in the coating of the stage, the asphalt-based coating agent is subjected to pre-oxidation treatment at low temperature, so that the structure of a carbon layer is disordered and is close to the property of hard carbon, and the multiplying power and the cycle performance of the material are improved;
and in the second stage, inert atmosphere is adopted, the heat treatment temperature in the second stage is 800-1050 ℃, and the heat treatment time is 2-4 hours. The stage is a conventional asphalt carbonization cracking step, an amorphous carbon layer is formed to relieve the expansion of an internal structure, and the purpose of maintaining the structural stability of the material is achieved;
therefore, the invention has the following beneficial effects:
(1) the core of the silicon-carbon cathode material of the lithium ion battery is secondary particles formed by crosslinking nano silicon and nano silicon oxide through a conductive agent, the volume stress is relieved through material nanocrystallization, the respective advantages of the nano silicon and the silicon oxide are combined, the conductive agent playing a crosslinking role can relieve the volume expansion of a silicon-based material while enhancing the conductivity of the material, in addition, the use of a matrix material is avoided, and the size of the material is more controllable; the outer layer is an amorphous carbon layer, the multiplying power and the cycle performance of the material are improved through the structural disorder of the carbon layer, and meanwhile, compared with pure hard carbon coating, the first effect of the composite material is not reduced, and the comprehensive performance is better;
(2) the preparation method has the advantages of simple operation, low cost, no pollution and easy industrialization.
Drawings
Fig. 1 is a schematic structural diagram of a silicon-carbon negative electrode material of a lithium ion battery of the invention.
Fig. 2 is an X-ray diffraction pattern of the silicon-carbon negative electrode material of the lithium ion battery prepared in example 1.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Adding 15kg of deionized water, 0.3kg of micron silicon powder, 2.7kg of micron silicon monoxide powder and 0.1kg of dispersant PVP into a stirring tank in sequence, stirring for 2h, starting a diaphragm pump, pumping the slurry into a sand mill for sanding, sampling every 2h to test the granularity of the slurry, adding 2kg of carbon nanotube conductive liquid with the mass fraction of 5% when the granularity D50 is less than 100nm, and continuing sanding for 2h to obtain the final slurry;
(2) spray drying the slurry obtained in the step (1), wherein the spray drying is carried out by adopting a spray dryer; the spray dryer is a closed circulation system, and the circulating gas is N2The inlet temperature of the spray dryer is set to 210 ℃, the outlet temperature is set to 100 ℃, the frequency of the atomizer is 300Hz, and the dried powder is subjected to airflow classification to obtain secondary particle powder with the D50 of 5-6 mu m;
(3) adding the secondary particle powder obtained in the step (2) and coal tar into a kneader according to the mass ratio of 5:1, kneading for 3 hours at 200 ℃, and naturally cooling to obtain kneaded powder;
(4) putting the powder kneaded in the step (3) into a tubular atmosphere furnace, introducing oxygen, raising the temperature to 200 ℃ at the speed of 2 ℃/min, preserving the heat for 6h, and switching to N2Continuously heating to 1000 ℃ at the speed of 5 ℃/min, and preserving heat for 3h to obtain the lithium ion battery silicon-carbon negative electrode material with the granularity D50 of 15 mu m and the structure as shown in figure 1, wherein the X-ray diffraction spectrum of the material is as shown in figure 2, and the product mainly shows the peak of crystal Si and amorphous SiOxBroad peak of (2).
Example 2
(1) Adding 15kg of deionized water, 0.5kg of micron silicon powder, 2.8kg of micron silica powder and 0.2kg of dispersant CTAB into a stirring tank in sequence, stirring for 2 hours, starting a diaphragm pump, pumping the slurry into a sand mill for sanding, sampling every 2 hours to test the granularity of the slurry, stopping sanding when the granularity D50 is less than 80nm, adding 4kg of graphene conductive liquid with the mass fraction of 3%, and continuing sanding for 2 hours to obtain the final slurry;
(2) spray drying the slurry obtained in the step (1), wherein the spray drying is carried out by adopting a spray dryer; the spray dryer is a closed circulation system, and the circulating gas is N2Carrying out airflow classification on the dried powder material to obtain secondary particle powder with the D50 particle size of about 8 microns, wherein the inlet temperature of the spray dryer is set to be 240 ℃, the outlet temperature of the spray dryer is set to be 105 ℃, and the frequency of an atomizer is 350 Hz;
(3) adding the secondary particle powder obtained in the step (2) and coal-based asphalt into a kneader according to the mass ratio of 15:1, kneading for 2 hours at 180 ℃, and naturally cooling to obtain kneaded powder;
(4) adding the powder obtained in the step (3) into a box-type atmosphere furnace, introducing oxygen, raising the temperature to 350 ℃ at the speed of 2 ℃/min, preserving the heat for 3h, and switching to N2And continuously heating to 800 ℃ at the speed of 5 ℃/min, and preserving the heat for 4h to obtain the silicon-carbon negative electrode material of the lithium ion battery, wherein the particle size D50 is 13.9 mu m and the structure of the silicon-carbon negative electrode material is shown in figure 1.
Example 3
(1) Adding 15kg of deionized water, 0.3kg of micron silicon powder, 3kg of micron silica powder and 0.2kg of dispersing agent PVP into a stirring tank in sequence, stirring for 2h, starting a diaphragm pump, pumping the slurry into a sand mill for sanding, adding 3kg of carbon nano tube conductive liquid with the mass fraction of 5%, and continuing sanding for 2h to obtain final slurry;
(2) spray drying the slurry obtained in the step (1), wherein the spray drying is carried out by adopting a spray dryer; the spray dryer is a closed circulation system, and the circulating gas is N2The inlet temperature of the spray dryer is set to 210 ℃, the outlet temperature is set to 100 ℃, the frequency of the atomizer is 250Hz, and the dried powder is subjected to airflow classification to obtain secondary particle powder with the D50 of 3-5 mu m;
(3) adding the secondary particle powder obtained in the step (2), petroleum asphalt and phenolic resin into a kneader according to the mass ratio of 15:1:1, kneading for 2 hours at the temperature of 250 ℃, and naturally cooling to obtain kneaded powder;
(4) and (3) adding the powder obtained in the step (3) into a tubular atmosphere furnace, introducing oxygen, raising the temperature to 400 ℃ at the speed of 2 ℃/min, preserving the heat for 1h, switching to argon, continuing raising the temperature to 1050 ℃ at the speed of 5 ℃/min, and preserving the heat for 2h to obtain the silicon-carbon cathode material of the lithium ion battery, wherein the structure of the silicon-carbon cathode material with the granularity D50 of 14.8 mu m is shown in figure 1.
COMPARATIVE EXAMPLE 1 (different core materials)
The difference between the comparative example 1 and the example 1 is that the inner core of the silicon-carbon negative electrode material of the lithium ion battery is a secondary particle formed by crosslinking nano silicon through a conductive agent, and the rest structure and the preparation process are completely the same.
COMPARATIVE EXAMPLE 2 (core materials different)
The difference between the comparative example 2 and the example 1 is that the inner core of the silicon-carbon negative electrode material of the lithium ion battery is a secondary particle formed by crosslinking nano-silicon oxide through a conductive agent, and the rest structure and the preparation process are completely the same.
Comparative example 3 (amorphous carbon layer)
The difference between the comparative example 3 and the example 1 is that the step (3) is omitted, the lithium ion battery silicon-carbon negative electrode material is provided with an amorphous carbon layer without an outer shell, and the rest structure and the preparation process are completely the same.
COMPARATIVE EXAMPLE 4 (commercial silicon carbon Material)
Comparative example 4 uses a commercial silicon carbon material with a core-shell structure in which the carbon layer directly coats the SiO.
The lithium ion battery silicon-carbon cathode materials prepared in examples 1-3 and comparative examples 1-4 are assembled into a button battery for electrochemical performance test analysis, and the specific scheme is as follows: the preparation material, the conductive agent SP, the conductive agent VGCF and the adhesive LA136 are mixed according to the ratio of 75:5:10:10 to prepare a button cell with the model number of 2032, the counter electrode is a lithium sheet, the diaphragm is a Celgard 2400 microporous polypropylene film, the charge-discharge cutoff voltage is 0.005-1.5V, the discharge rate is 0.1C and 0.02C, and the charge rate is 0.1C. The test results are shown in table 1:
TABLE 1 test results
Figure BDA0002458428560000061
As can be seen from table 1, it can be seen from comparative example 1 and comparative example 4 that the reversible capacity, the first efficiency and the cycling stability of the lithium ion battery assembled by using the battery silicon carbon negative electrode material of the present invention are effectively improved compared with the currently commercialized silicon carbon material, and from comparative example 1 and comparative examples 1-2, only the battery silicon carbon negative electrode material added with nano silicon and nano silicon monoxide has excellent performance, and the absence of any one of the materials can cause a great reduction in the cycling performance of the material; as can be seen by comparing example 1 and comparative example 3, the absence of an outer amorphous carbon layer results in a decrease in the overall electrical performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (9)

1. A preparation method of a lithium ion battery silicon-carbon negative electrode material is characterized in that the lithium ion battery silicon-carbon negative electrode material is of a core-shell structure, and the inner core of the lithium ion battery silicon-carbon negative electrode material is secondary particles formed by crosslinking nano silicon and nano silicon monoxide through a conductive agent; the shell of the lithium ion battery silicon-carbon cathode material is an amorphous carbon layer, and is characterized by comprising the following steps of:
(1) adding a dispersing agent and deionized water into nano silicon and nano silicon monoxide, and sanding to obtain slurry;
(2) adding a conductive agent solution into the slurry, uniformly stirring, and performing spray drying to obtain secondary particle powder;
(3) adding a carbon source into the secondary particle powder, kneading, and performing heat treatment to obtain the silicon-carbon cathode material of the lithium ion battery;
the heat treatment is divided into two stages, wherein the first stage adopts oxygen, air or mixed atmosphere of oxygen and inert gas; the heat treatment temperature of the first stage is 200-400 ℃, and the heat treatment time is 1-6 h; and in the second stage, inert atmosphere is adopted, the heat treatment temperature in the second stage is 800-1050 ℃, and the heat treatment time is 2-4 hours.
2. The method for preparing the silicon-carbon anode material of the lithium ion battery according to claim 1, wherein the conductive agent is carbon nanotubes, graphene or carbon nanofibers; the conductive agent is in a linear, tubular, sheet or net structure.
3. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the particle size of the nano silicon and the nano silicon monoxide is 80-120 nm; the mass ratio of the nano silicon to the nano silicon monoxide is 1: (6-10).
4. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the mass ratio of the conductive agent to the nano-silicon is 1: (1-8).
5. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the ratio of the amorphous carbon layer to the total mass of the nano silicon and the nano silicon monoxide is 1: (5-20).
6. The preparation method of the silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the particle size D50 of the silicon-carbon negative electrode material for the lithium ion battery is 1-20 μm.
7. The preparation method of the silicon-carbon anode material of the lithium ion battery according to claim 1, wherein in the step (1), the dispersant is one or more of polyvinylpyrrolidone, polyethylene, polypropylene, polystyrene and cetyl trimethyl ammonium bromide;
the mass ratio of the dispersing agent to the nano silicon is 1: (1.5-4);
the mass ratio of the conductive agent to the nano silicon is 1: (1-8);
the ratio of the deionized water to the total mass of the nano silicon and the nano silicon monoxide is (4-10): 1.
8. the preparation method of the silicon-carbon anode material of the lithium ion battery according to claim 1, wherein in the step (2), spray drying is performed by using a spray dryer; the spray dryer is a closed circulation system, and the circulating gas is N2(ii) a The inlet temperature of the spray dryer is 200-240 ℃, and the outlet temperature of the spray dryer is 250-340 Hz; the particle size D50 of the secondary particle powder is controlled to be 3-20 mu m.
9. The method for preparing the silicon-carbon anode material of the lithium ion battery according to claim 1, wherein in the step (3), the carbon source is one or more of coal-series pitch, petroleum-series pitch and a mixture of the coal-series pitch and the resin carbon material.
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