CN114171722A - Preparation method of silicon-carbon composite material - Google Patents

Preparation method of silicon-carbon composite material Download PDF

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Publication number
CN114171722A
CN114171722A CN202010950479.0A CN202010950479A CN114171722A CN 114171722 A CN114171722 A CN 114171722A CN 202010950479 A CN202010950479 A CN 202010950479A CN 114171722 A CN114171722 A CN 114171722A
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silicon
carbonization
composite material
coating material
carbon
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邱新平
张文广
郑曦
李慧玉
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Beijing Qingchuang Silicon Valley Technology Co ltd
Tsinghua University
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Beijing Qingchuang Silicon Valley Technology Co ltd
Tsinghua University
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    • 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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The disclosure relates to a preparation method of a silicon-carbon composite material, which comprises the following steps: the first step is as follows: mixing nano silicon with a pyrolytic carbon source or an aqueous solution thereof, so as to coat the carbon source on the surface of the nano silicon to obtain a first pre-coating material; the second step is as follows: heating the first coating material to 500-650 ℃ for pre-carbonization to obtain a first coating material; the third step: repeating the first and second steps to form a second cladding material; the fourth step: and putting the second coating material into the middle part of a high-temperature furnace for carbonization, adding metallurgical silicon with the particle size of 1 mu m to 1mm as a reduction protective agent into a gas inlet end and a gas outlet end of the furnace, and heating the mixture to 950 to 1000 ℃ under an inert atmosphere for high-temperature carbonization for 4 to 8 hours to obtain the silicon-carbon composite material. The metallurgical silicon powder disclosed by the invention can prevent the silicon-carbon composite material from being oxidized in carbonization, is low in cost and can be used for multiple times, and is suitable for large-scale production.

Description

Preparation method of silicon-carbon composite material
Technical Field
The present disclosure relates to a method of preparing a composite material. Specifically, the disclosure relates to a preparation method of a carbon-silicon composite material, and particularly relates to a preparation method of a silicon-carbon composite material for a lithium ion battery cathode.
Background
In the field of lithium ion batteries, in order to improve energy density, electrode materials with high specific capacity need to be developed. The nano silicon material becomes the most promising next-generation cathode material due to higher specific capacity than graphite, but the problems of unstable SEI film, poor conductivity and the like exist in the silicon material, so that the charge-discharge cycle life of the battery is short. For this reason, a method of silicon-carbon recombination is required to improve the problems of instability and poor conductivity of the SEI film of the silicon material.
In the preparation process of the silicon-carbon composite material in the prior art, silicon is easy to generate oxidation reaction in the high-temperature carbonization process of the silicon-carbon composite material, so that the high specific capacity of the silicon-carbon composite material cannot be exerted. Furthermore, the presence of elements such as the impurity H, O introduced from the carbon source also deteriorates the performance of the anode material. When the carbonization temperature is lowered in order to reduce the oxidation reaction of silicon, the content of these impurity elements becomes higher.
Disclosure of Invention
In view of the problems in the prior art, the inventors of the present disclosure have found through repeated experiments that a small amount of metallurgical silicon is added in the carbonization step to remove a trace amount of oxygen, thereby preventing oxidation of the coated silicon, and the metallurgical silicon is easily removed in a subsequent process. And has accomplished the present disclosure on this basis.
An object of the present disclosure is to provide a method for preparing a carbon-silicon composite material to prevent silicon in the composite material from being oxidized.
According to one aspect of the present disclosure, there is provided a method for preparing a silicon-carbon composite material, the method comprising:
the first step is as follows: mixing nano silicon with a pyrolytic carbon source or an aqueous solution thereof, so as to coat the carbon source on the surface of the nano silicon to obtain a first pre-coating material;
the second step is as follows: heating the first coating material to 500-650 ℃ for pre-carbonization to obtain a first coating material;
the third step: repeating the first and second steps to form a second cladding material;
the fourth step: and putting the second coating material into the middle part of a high-temperature furnace for carbonization, adding metallurgical silicon powder with the particle size of 1 mu m to 1mm as a reduction protective agent into the gas inlet end and the gas outlet end of the furnace, and heating the mixture to 950 to 1000 ℃ under an inert atmosphere for high-temperature carbonization for 4 to 8 hours to obtain the silicon-carbon composite material.
Advantageous effects
The method solves the problems of poor conductivity, large volume expansion and easy oxidation due to high-temperature carbonization of the nano-silicon material, and can realize the following effects:
(1) by multiple times of pyrolytic carbon coating and pre-carbonization, the conductivity of the silicon-carbon composite negative electrode material can be improved and the growth of an SEI film on the surface of the silicon can be prevented;
(2) the metallurgical silicon is added in the high-temperature carbonization process, so that the high temperature can be ensured to be enough to remove non-carbon impurity elements in the pyrolytic carbon; meanwhile, the silicon element in the silicon-carbon composite material is prevented from being oxidized by trace oxygen, and the characteristic of high specific capacity of the silicon-carbon material is ensured.
Drawings
FIG. 1 is a photograph showing the metallurgical silicon powder of example 1 before and after the test, wherein a is before the test and b is after the test.
FIG. 2 is a bar graph of the mass change of metallurgical silicon powder before and after the test in example 1.
Fig. 3 is a graph showing the first discharge capacity of batteries prepared from the carbon silicon composite materials in example 1 and comparative example 1.
Fig. 4 is a graph showing the change in the cycle capacity of batteries prepared from the carbon-silicon composite materials in example 1 and comparative example 1.
Fig. 5 is a graph showing the change in cycle efficiency of batteries prepared from the carbon silicon composite materials in example 1 and comparative example 1.
Fig. 6 is an electron micrograph showing the morphology of a silicon carbon composite without reduction protection prepared from comparative example 1.
Fig. 7 is a graph representing an elemental content analysis of a silicon carbon composite material without reduction protection prepared by comparative example 1.
FIG. 8 is an electron micrograph showing the morphology of the reduction-protected silicon carbon composite prepared from example 1.
Fig. 9 is a graph showing an elemental content analysis of the reduction-protected silicon carbon composite prepared in example 1.
Detailed Description
To make the features and effects of the present invention comprehensible to those having ordinary knowledge in the art, general description and definitions are made with respect to terms and phrases mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the precision of the number of significant digits of the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.
In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that a sub-group of all elements or any individual element within a Markush group or list of options may also be used to describe the invention. For example, if X is described as "selected from the group consisting of1、X2And X3The group "also indicates that X has been fully described as X1Is mainlySheet and X are X1And/or X2Claim (5). Furthermore, where Markush group or option terms are used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all elements or individual elements within the Markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of1、X2And X3Group consisting of "and Y is described as" selected from Y1、Y2And Y3The group "formed indicates that X has been fully described as X1Or X2Or X3And Y is Y1Or Y2Or Y3Claim (5).
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.
According to one embodiment of the present disclosure, there is provided a method for preparing a silicon-carbon composite material, the method including:
the first step is as follows: mixing nano silicon with a pyrolytic carbon source or an aqueous solution thereof, so as to coat the carbon source on the surface of the nano silicon to obtain a first pre-coating material;
the second step is as follows: heating the first coating material to 500-650 ℃ for pre-carbonization to obtain a first coating material;
the third step: repeating the first and second steps to form a second cladding material;
the fourth step: and putting the second coating material into the middle part of a high-temperature furnace for carbonization, adding metallurgical silicon powder with the particle size of 1 mu m to 1mm as a reduction protective agent into the gas inlet end and the gas outlet end of the furnace, and heating the mixture to 950 to 1000 ℃ under an inert atmosphere for high-temperature carbonization for 4 to 8 hours to obtain the silicon-carbon composite material.
According to the preparation method, the carbon coating layer can be formed on the surface of the nano silicon after the first step, the second step and the third step so as to improve the conductivity, prevent the electrolyte from directly contacting with the nano silicon, prevent an SEI (solid electrolyte interphase) film from being formed on the surface of the silicon and improve the first coulombic efficiency; in the fourth step of high-temperature carbonization, the metallurgical silicon is added to absorb trace oxygen brought in the furnace and gas and brought in by insufficient furnace body tightness, so that the silicon-carbon composite material is prevented from being oxidized. Therefore, after the silicon-carbon composite material is carbonized at high temperature, the characteristic of high specific capacity of the silicon material can be kept, and elements such as impurity H, O can be removed to prevent the performance degradation of the negative electrode material.
According to one embodiment of the present disclosure, in the first and third steps, the particle size of the nano-silicon is 1nm to 200 nm; the pyrolytic carbon source comprises one or more selected from glucose, sucrose, starch, sodium stearate, calcium stearate, asphalt and phenolic resin.
By using the nano silicon and the pyrolytic carbon source, the uniformly coated coating material with proper particle size can be obtained, so that the cathode material with excellent performance is obtained. When the grain diameter of the nano silicon material is less than 1nm, the nano silicon material is extremely difficult to prepare and is extremely easy to agglomerate; when the particle size of the nano silicon material is larger than 200nm, the volume change of the nano silicon material is overlarge in the charging and discharging process, so that the particles are broken, and the electrical property is reduced.
According to one embodiment of the present disclosure, the amount of the carbon source mixed at each time in the first and third steps is 10% to 50%, preferably 20% to 30%, of the mass of the nano silicon.
By using the nano silicon and the pyrolytic carbon source in a mixed ratio, the uniformly coated coating material with proper particle size can be obtained, so that the cathode material with excellent performance is obtained. When the mass of the added carbon source is less than 10% of the mass of the nano silicon, the coating is insufficient, so that the conductivity of the composite material is reduced and the electrical property is reduced; when the mass of the added carbon source is more than 50% of the mass of the nano silicon, the coating layer is too thick, and the capacity performance of the silicon material is not obvious, namely the capacity of the negative electrode material is reduced.
According to one embodiment of the present disclosure, in the fourth step, the metallurgical silicon powder has a particle size of 10 μm to 300 μm; more preferably 200 μm; and in the high-temperature carbonization process, the introduced inert gas is high-purity nitrogen or argon.
According to the preparation method, non-carbon impurity elements in pyrolytic carbon can be effectively removed, simultaneously, metallurgical silicon powder after reaction can be easily removed, impurities can not be introduced, and therefore the uniform and compact multilayer carbon-coated material with excellent electrical property can be effectively obtained.
Example 1: preparation of carbon-silicon composite material
A) Mixing self-made nano silicon and low-temperature asphalt in a ratio of 2: 3, heating to 120 ℃, and stirring in a high-speed dispersion machine for 4 hours to obtain a first pre-coating material;
B) then, heating the first coating material to 500-650 ℃ under nitrogen to perform pre-carbonization;
C) the pre-carbonized product was then mixed again with pitch at a ratio of 9: 1, heating to 120 ℃, and stirring in a high-speed dispersion machine for 2 hours to obtain a second coating material;
D) and putting the second coating material into the middle part of a high-temperature furnace for carbonization, adding metallurgical silicon with the particle size of 500 mu m as a reduction protective agent into the gas inlet end and the gas outlet end of the furnace, and heating the mixture to 950-1000 ℃ in an inert atmosphere for high-temperature carbonization for 4-8h to obtain the silicon-carbon composite material.
Example 2: change of reduction protectant before and after high-temperature carbonization
The metallurgical silicon powder of example 1 was tested before and after the test, and fig. 1 and 2 show the change of color and quality of the metallurgical silicon powder before and after the test (a is before the test and b is after the test). As can be seen from FIG. 1, the metallurgical silicon changed color from light black to dark black after the carbonization temperature rise test. Meanwhile, as can be seen from fig. 2, the mass of metallurgical silicon increased from 9.426g to 12.417g after the carbonization temperature rise test, and the increased 2.91g is caused by partial oxidation of silicon into silicon oxide.
Comparative example 1
A composite material was prepared according to the same silicon carbon composite preparation process as example 1, except that metallurgical silicon was not added for reduction protection in step D).
Experimental example 1
The carbon-silicon composite materials prepared in example 1 and comparative example 1 were subjected to performance tests using the prepared silicon-carbon composite materials, respectively, using the same battery assembly process and test process.
Specifically, the carbon-silicon composite materials prepared in example 3-1 and comparative example 3-2 were mixed with deionized water, CMC, sodium alginate, and conductive carbon black, coated, and dried to prepare a negative electrode of a lithium ion battery, and a test cell was prepared using a lithium sheet as a counter electrode.
After the first charge and discharge, a cycling test was performed at 0.1C rate, and its electrochemical properties are shown in fig. 3.
As can be seen from fig. 3, the cell capacity of the silicon carbon composite with metallurgical silicon added as reduction protection was 1600mAh/g, while the cell capacity of the silicon carbon composite without metallurgical silicon addition protection was 1050 mAh/g. The difference in cell capacity should be due primarily to the fact that under unreduced protection, part of the hollow silicon is oxidized to silicon oxide, resulting in this part not contributing to the cell capacity.
The electrochemical cycle performance of the composite materials of example 1 and comparative example 1 was further measured, and the results are shown in fig. 4. As can be seen from fig. 4, the capacity of the battery assembled by the silicon-carbon composite material without reduction protection decays faster as the cyclic charge and discharge progresses. This indicates that the carbon-silicon composite material of comparative example 1 has poor cycle performance due to the presence of silicon oxide.
The cell cycle efficiencies of the carbon silicon composite materials prepared in example 1 and comparative example 1 were compared, and the results are shown in fig. 5. As can be seen from fig. 5, the first charge-discharge efficiency of the material without reduction protection is only 83.64%, which is much lower than that of the silicon-carbon composite material with reduction protection.
Experimental example 4
The carbon-silicon composite materials prepared in example 1 and comparative example 1 were examined in a scanning electron microscope, and the results thereof are shown in fig. 6 and 8. The results of the elemental analysis are shown in FIG. 7, FIG. 9 and tables 1-2 below.
Element(s) wt％ wt％Sigma
C 22.78 0.13
O 38.76 0.14
Si 38.45 0.15
Total amount: 100.00
TABLE 1 elemental content of silicon-carbon composites without reduction protection
Element(s) wt％ wt％Sigma
C 35.70 0.16
O 10.29 0.09
Si 54.01 0.16
Total amount: 100.00
TABLE 2 element content of silicon-carbon composite with reduction protection
According to the above experimental examples, it can be seen that the oxygen content of the silicon carbon composite material of example 3-1 without adding metallurgical silicon is 38.76%, while the characterization data of the silicon carbon composite material of example 3-2 with adding metallurgical silicon shows that the oxygen content is only 10.29%. The oxygen content of the silicon-carbon composite material protected by the metallurgical silicon can be greatly controlled.
The above embodiments are merely exemplary in nature and are not intended to limit the claimed embodiments or the application or uses of such embodiments. In this document, the term "exemplary" represents "as an example, instance, or illustration. Any exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.
In addition, while at least one exemplary embodiment or comparative example has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations are possible. It should also be appreciated that the embodiments described herein are not intended to limit the scope, applicability, or configuration of the claimed subject matter in any way. Rather, the foregoing implementations will provide those of ordinary skill in the art with a convenient road map for implementing the described embodiment or embodiments. Further, various changes may be made in the function and arrangement of elements without departing from the scope defined in the claims, which includes known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims (6)

1. A method for preparing a silicon-carbon composite material, the method comprising:
the first step is as follows: mixing nano silicon with a pyrolytic carbon source or an aqueous solution thereof, so as to coat the carbon source on the surface of the nano silicon to obtain a first pre-coating material;
the second step is as follows: heating the first coating material to 500-650 ℃ for pre-carbonization to obtain a first coating material;
the third step: repeating the first and second steps to form a second cladding material;
the fourth step: and putting the second coating material into the middle part of a high-temperature furnace for carbonization, adding metallurgical silicon powder with the particle size of 1 mu m to 1mm as a reduction protective agent into the gas inlet end and the gas outlet end of the furnace, and heating the mixture to 950 to 1000 ℃ under an inert atmosphere for high-temperature carbonization for 4 to 8 hours to obtain the silicon-carbon composite material.
2. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,
in the first and third steps, the particle size of the nano-silicon is 1nm to 200 nm; the pyrolytic carbon source comprises one or more selected from glucose, sucrose, starch, sodium stearate, calcium stearate, asphalt and phenolic resin.
3. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,
in the first and third steps, the amount of the carbon source mixed at each time is 10% to 50% of the mass of the nano silicon.
4. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,
in the first and third steps, the amount of the carbon source mixed at each time is 20 to 30% of the mass of the nano silicon.
5. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,
in the fourth step, the particle size of the metallurgical silicon powder is 10-300 μm; and in the high-temperature carbonization process, the introduced inert gas is high-purity nitrogen or argon.
6. The method of claim 5, wherein the first and second light sources are selected from the group consisting of,
in the fourth step, the particle size of the metallurgical silicon powder is 200 μm.
CN202010950479.0A 2020-09-11 2020-09-11 Preparation method of silicon-carbon composite material Pending CN114171722A (en)

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