CN116936811A - Negative electrode material, preparation method and application thereof - Google Patents
Negative electrode material, preparation method and application thereof Download PDFInfo
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- CN116936811A CN116936811A CN202311196821.2A CN202311196821A CN116936811A CN 116936811 A CN116936811 A CN 116936811A CN 202311196821 A CN202311196821 A CN 202311196821A CN 116936811 A CN116936811 A CN 116936811A
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- amorphous carbon
- negative electrode
- carbon
- anode material
- electrode material
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 52
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 41
- 238000009826 distribution Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000002441 reversible effect Effects 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 90
- 238000000034 method Methods 0.000 claims description 33
- 238000011282 treatment Methods 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 24
- 230000004913 activation Effects 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 18
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 17
- 239000007833 carbon precursor Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
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- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 19
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- 239000010439 graphite Substances 0.000 abstract description 7
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- 239000002210 silicon-based material Substances 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
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- 239000002194 amorphous carbon material Substances 0.000 description 10
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- 239000007789 gas Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- PUUOOWSPWTVMDS-UHFFFAOYSA-N difluorosilane Chemical compound F[SiH2]F PUUOOWSPWTVMDS-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 230000002687 intercalation Effects 0.000 description 1
- ZGUQQOOKFJPJRS-UHFFFAOYSA-N lead silicon Chemical compound [Si].[Pb] ZGUQQOOKFJPJRS-UHFFFAOYSA-N 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
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- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a negative electrode material, a preparation method and application thereof, and relates to the technical field of electrode materials, wherein the negative electrode material mainly comprises nano silicon particles andamorphous carbon composition, negative electrode material structure Si/C m (m is more than or equal to 0.25 and less than or equal to 4), the average sphericity phi s of the anode material is between 0.6 and 1.0, the granularity distribution K90 is between 0.9 and 1.4, and the median particle diameter D50 is between 2 and 9 mu m. The invention solves the technical problem that the energy density of the battery is not beneficial to improvement due to the fact that the silicon material is compounded with the carbon material or graphite with irregular morphology when the traditional silicon anode material is prepared, achieves the technical effects that silicon and carbon are uniformly distributed in the anode material, has higher first reversible capacity, higher first efficiency and lower charging volume expansion effect, and can effectively improve the energy density of the lithium ion battery and improve the first efficiency when being applied to the lithium ion secondary battery.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a negative electrode material, and a preparation method and application thereof.
Background
With the development of new energy electric vehicles and electric aircrafts, the demand for high-energy density electrode materials is more and more urgent. Currently, the theoretical capacity of the graphite anode material is only 372 mA.h/g, and the capacity of the commercial graphite is already close to the theoretical capacity; among the numerous negative electrode materials, silicon materials have the highest theoretical lithium storage capacity, forming Li at room temperature 15 Si 4 The theoretical capacity can reach 3579 mA.h/g, and the energy density of the battery can be greatly improved by applying the silicon material to the battery cathode.
The silicon material has high capacity and simultaneously has huge charging volume expansion, and the excessive volume expansion easily causes particle breakage and pulverization, and the solid electrolyte membrane grows in a large quantity, so that the capacity of the cathode is finally attenuated, and the capacity of the battery is attenuated. At present, the preparation of the silicon anode material is carried out by compounding the silicon material with the irregular-morphology carbon material or graphite, so that the effect of reducing the volume expansion of the silicon material is achieved, but the irregular-morphology carbon material is poor in fluidity and coating uniformity, and the irregular-morphology silicon material particles are easy to crush during cold pressing of the electrode plate, so that the energy density of the battery is not beneficial to improvement.
In view of this, the present invention has been made.
Disclosure of Invention
One of the purposes of the invention is to provide a cathode material which has higher sphericity and more concentrated particle size distribution, can lead silicon and carbon to be distributed in the cathode material more uniformly, has higher first reversible capacity and first efficiency, and has lower charging volume expansion effect, thereby being beneficial to improving the energy density of a lithium ion secondary battery and improving the first efficiency.
The second purpose of the invention is to provide a preparation method of the anode material, which is simple in process, suitable for industrial production, capable of improving the first efficiency and the first reversible capacity of the anode material and enabling the anode material to have a lower charging volume expansion effect.
The invention further aims to provide an application of the anode material, which can effectively improve the energy density and the first efficiency of the lithium ion secondary battery and can obtain a remarkable application effect.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, a negative electrode material comprises nano-silicon particles and amorphous carbon;
the structure of the anode material is Si/C m Wherein m is more than or equal to 0.25 and less than or equal to 4;
the granularity distribution K90 of the anode material is between 0.9 and 1.4;
the average sphericity phi s of the anode material is between 0.6 and 1.0;
the median particle diameter D50 of the negative electrode material is 2-9 mu m.
Further, the specific surface area of the negative electrode material is 0.5-10 m/g.
Further, the average sphericity of the amorphous carbon is between 0.6 and 1.0;
preferably, the amorphous carbon has a median particle diameter D50 of 2-8 μm;
preferably, the amorphous carbon has a particle size distribution K90 of 0.8-1.8;
preferably, the specific surface area of the amorphous carbon is 500-3000 m/g.
Further, the pore volume of the amorphous carbon is more than or equal to 0.5cm, and the amorphous carbon is less than or equal to g;
preferably, the pore structure of the amorphous carbon includes at least two of micropores, mesopores, and macropores;
preferably, the volume fraction of the micropores is 10-95%;
preferably, the volume fraction of the mesopores is 10-95%;
preferably, the volume fraction of macropores is less than 10%.
Further, the nano silicon particles are amorphous silicon;
preferably, the average particle size D50 of the nano-silicon particles is less than 50nm;
preferably, the nano silicon particles account for 20-80 wt% of the anode material.
In a second aspect, a method for preparing the anode material according to any one of the above claims, includes the steps of:
(a) Preparing amorphous carbon with average sphericity more than or equal to 0.6;
(b) Pyrolyzing a silane compound in the pore structure of the amorphous carbon to deposit nano silicon particles in the pore structure of the amorphous carbon to obtain a silicon carbon precursor;
(c) And (3) passivating the silicon-carbon precursor in the step (b) to obtain the anode material.
Further, the method for preparing amorphous carbon comprises the following steps:
pre-carbonizing a carbon source material to obtain a pre-carbide;
the pre-carbide is carbonized, crushed and activated to obtain amorphous carbon;
preferably, the carbon source material comprises at least one of glucose, fructose, galactose, lactose, sucrose, maltose, rice starch, mung bean starch, wheat starch, tapioca starch, corn starch, cellulose and phenolic resin;
preferably, the method of pre-carbonization comprises at least one of solvothermal reaction, low temperature carbonization and spray drying;
preferably, the average sphericity of the pre-carbide is more than or equal to 0.6;
preferably, the activation treatment includes at least one of a physical activation method and a chemical activation method;
preferably, the gas used in the physical activation method includes at least one of steam, air and carbon dioxide;
preferably, the chemical agent of the chemical activation method includes at least one of phosphoric acid, zinc chloride, potassium hydroxide, and sodium hydroxide.
In a third aspect, a negative electrode material according to any one of the preceding claims is used in a lithium ion secondary battery.
Further, when the lithium ion secondary battery is discharged to 0.005V with constant current and then charged to 1.5V with constant current, the first reversible capacity of the lithium ion secondary battery is more than or equal to 1700 mA.h/g, and the first efficiency is more than or equal to 92%.
Further, the first efficiency of the lithium ion secondary battery is 81% or more when charged to a voltage of 0.8V at a constant current.
Further, the first efficiency of the lithium ion secondary battery is 66% or more when charged to a voltage of 0.6V at a constant current.
Compared with the prior art, the invention has at least the following beneficial effects:
the negative electrode material provided by the invention has higher sphericity and more concentrated particle size distribution, nano silicon particles can be uniformly distributed in amorphous carbon, and compared with the negative electrode material with irregular morphology, the negative electrode material with high sphericity has higher compressive strength, and can bear higher pressure in the cold pressing process for preparing the electrode plate, so that the risk of crushing the particles is avoided; the negative electrode material provided by the invention has higher first efficiency and first reversible capacity, the first reversible capacity can reach more than 1700 mA.h/g in a lithium ion battery test system, the first efficiency can reach more than 92%, and the negative electrode material has higher compressive strength and lower charging volume expansion effect after being mixed with graphite.
The preparation method of the anode material provided by the invention is simple in process, suitable for industrial production, capable of improving the first efficiency and the first reversible capacity of the anode material and enabling the anode material to have a low charging volume expansion effect.
The application of the negative electrode material provided by the invention can effectively improve the energy density of the lithium ion secondary battery and the first efficiency, and has an outstanding application effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of an amorphous carbon material of example 1 of the present invention at a magnification of 1000;
FIG. 2 is a scanning electron microscope image of an amorphous carbon material 30000 times as provided in example 1 of the present invention;
FIG. 3 is an XRD diffraction pattern of an amorphous carbon material provided in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the negative electrode material of example 1 of the present invention at a magnification of 1000;
FIG. 5 is a scanning electron microscope image of 30000 times of the anode material provided in example 1 of the present invention;
FIG. 6 is an ion milling section scanning electron microscope and energy spectrum of a pole piece prepared from the negative electrode material provided in example 1 of the present invention;
FIG. 7 is an XRD diffraction pattern of the anode material according to example 1 of the present invention;
FIG. 8 is a graph showing the initial charge/discharge characteristics of a lithium battery button cell of the negative electrode material obtained in test example 3 of the present invention;
fig. 9 is a plot of the initial charge/discharge dQ/dV of a lithium battery button cell of the negative electrode material obtained in test example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to a first aspect of the present invention, there is provided a negative electrode material comprising nano-silicon particles and amorphous carbon;
the structure of the anode material can be expressed as Si/C m Wherein, m is more than or equal to 0.25 and less than or equal to 4, m can be, for example, 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5 and 4, but is not limited to the above, and the value range of m defined by the invention is more favorable for obtaining the anode material with higher first reversible capacity and lower charge volume expansion; if the value of m is too large, the first reversible capacity of the material is too low, which is not beneficial to improving the energy density of the material; if the value of m is too small, the charge volume expansion of the material is too large, the side reaction is increased, and the capacity fading is accelerated;
the negative electrode material has a narrower particle size distribution, wherein the particle size distribution K90 is between 0.9 and 1.4, and typical but non-limiting particle size distribution K90 is, for example, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, wherein k90= (D90-D10)/D50;
the median particle diameter D50 of the negative electrode material may be 2-9 μm, and typical but non-limiting median particle diameters D50 thereof are, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm;
the average sphericity phis of the negative electrode material is between 0.6 and 1.0, and typical but non-limiting average sphericity phis is, for example, 0.6, 0.7, 0.8, 0.9, 1.0, wherein phis=ss/Sp, wherein Sp is the outer surface area of the non-spherical particles, ss is the outer surface area of the equal volume spheres.
The negative electrode material provided by the invention has higher sphericity and more concentrated particle size distribution, nano silicon particles can be uniformly distributed in amorphous carbon, and compared with the negative electrode material with irregular morphology, the negative electrode material with high sphericity has higher compressive strength, and can bear higher pressure in the cold pressing process for preparing the electrode plate, so that the risk of crushing the particles is avoided; the negative electrode material provided by the invention has higher first efficiency and first reversible capacity, the first reversible capacity can reach more than 1700 mA.h/g in a lithium ion battery test system, the first efficiency can reach more than 92%, and the negative electrode material has higher compressive strength and lower charging volume expansion effect after being mixed with graphite.
In a preferred embodiment, the median particle diameter D50 of the negative electrode material may be 4 to 7 μm, and typical but non-limiting median particle diameters D50 thereof are, for example, 4 μm, 5 μm, 6 μm, 7 μm, and may even more preferably be 5 to 6 μm.
In a preferred embodiment, the particle size distribution K90 of the negative electrode material may be more preferably 1.0 to 1.3, and still more preferably 1.1 to 1.2.
In a preferred embodiment, the specific surface area of the negative electrode material may be between 0.5 to 10 m/g, and the typical but non-limiting specific surface area thereof is, for example, 0.5 m/g, 1.0 m/g, 2.0 m/g, 3.0 m/g, 4.0 m/g, 5.0 m/g, 6.0 m/g, 7.0 m/g, 8.0 m/g, 9.0 m/g, 10 m/g, and may further preferably be 1 to 8 m/g, and still further preferably 2 to 4 m/g.
In the invention, the median particle diameter D50, the particle size distribution K90 and the specific surface area of the anode material are more favorable for further uniformly distributing silicon and carbon in the anode material, so that the first reversible capacity and the first efficiency of the anode material can be further improved, and the charging volume expansion effect can be further reduced.
In the present invention, the average sphericity of amorphous carbon is 0.6 to 1.0, for example, but not limited to, 0.6, 0.7, 0.8, 0.9, 1.0.
In a preferred embodiment, the amorphous carbon may have a median particle diameter D50 of 2 to 8 μm, which typical but non-limiting median particle diameter D50 is, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, more preferably 3 to 7 μm, still more preferably 4 to 6 μm.
In a preferred embodiment, the amorphous carbon may have a particle size distribution K90 of between 0.8 and 1.8, with typical but non-limiting particle size distribution K90 being, for example, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, more preferably 1.0 to 1.5, still more preferably 1.1 to 1.3, where k90= (D90-D10)/D50.
In a preferred embodiment, the specific surface area of amorphous carbon may be between 500 to 3000 m/g, for example, but not limited to 500 m/g, 600 m/g, 700 m/g, 800 m/g, 900 m/g, 1000 m/g, 1200 m/g, 1500 m/g, 2000 m/g, 2500 m/g, 3000 m/g, and may further preferably be 1000 to 2500 m/g, and still further preferably 1500 to 2000 m/g.
In the invention, the median particle diameter D50, the particle size distribution K90 and the specific surface area of the amorphous carbon are more favorable for further uniformly distributing silicon and carbon in the anode material, so that the first reversible capacity and the first efficiency of the anode material can be further improved, and the charging volume expansion effect can be further reduced.
In a preferred embodiment, the amorphous carbon may have a pore volume of 0.5cm or more, more preferably 0.8 to 2.5cm, and typically but not limited to 0.8cm, 0.9cm, 1.0cm, 1.2cm, 1.4cm, 1.6cm, 1.8cm, 2.0cm, 2.5cm, and even more preferably 1.0 to 2.0 cm.
In the present invention, the pore structure of amorphous carbon may include at least two of micropores, mesopores, and macropores, wherein the volume fraction of micropores may be 10 to 95%, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, but not limited thereto; the volume fraction of the mesopores may be 10 to 95%, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, but not limited thereto; the volume fraction of macropores may be less than 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, but not limited thereto.
In a preferred embodiment, the nano-silicon particles may be amorphous silicon, and the average particle size D50 thereof may be less than 50nm, for example, may be 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, but is not limited thereto.
In a preferred embodiment, the nano-silicon particles may comprise 20 to 80wt% of the negative electrode material, and typically but not limited to, for example, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, and may further preferably comprise 30 to 60wt%, and still further preferably comprise 40 to 50wt%.
In the invention, the type and the average granularity of the nano silicon particles are selected, and the ratio of the nano silicon particles in the anode material is more favorable for further improving the first efficiency and the first reversible capacity of the anode material, and is more favorable for further enabling the anode material to have lower charging volume expansion effect.
According to a second aspect of the present invention, there is provided a method for producing a negative electrode material according to any one of the above, comprising the steps of:
(a) Preparing amorphous carbon with average sphericity more than or equal to 0.6;
(b) Pyrolyzing a silane compound in the pore structure of amorphous carbon to deposit nano silicon particles in the pore structure of amorphous carbon to obtain a silicon-carbon precursor;
(c) And (3) passivating the silicon-carbon precursor in the step (b) to obtain the anode material.
The preparation method of the anode material provided by the invention is simple in process, suitable for industrial production, capable of improving the first efficiency and the first reversible capacity of the anode material and enabling the anode material to have a low charging volume expansion effect.
A typical preparation method of a negative electrode material includes the following steps:
(1) Providing amorphous carbon with average sphericity more than or equal to 0.6, wherein the amorphous carbon contains a porous structure;
(2) Fully contacting amorphous carbon with a silane compound, enabling the silane compound to enter a porous structure of the amorphous carbon for pyrolysis, and enabling nano silicon particles to be deposited in the porous structure of the amorphous carbon, so as to obtain a silicon-carbon precursor;
(3) And passivating the silicon-carbon precursor to obtain the anode material.
In a preferred embodiment, the process for the preparation of amorphous carbon having an average sphericity of not less than 0.6 comprises the steps of:
(1) carrying out solvothermal reaction on a carbon source material, washing and drying to obtain a pre-carbide with the average sphericity more than or equal to 0.6; or (2) carbonizing the carbon source material at low temperature, and performing wet ball milling to obtain a pre-carbide with the average sphericity more than or equal to 0.6; or (3) spray drying the carbon source material to obtain a pre-carbide with the average sphericity more than or equal to 0.6;
the carbon source material includes, but is not limited to, at least one of glucose, fructose, galactose, lactose, sucrose, maltose, rice starch, mung bean starch, wheat starch, tapioca starch, corn starch, cellulose, and phenolic resin;
solvents used in the above-described methods include, but are not limited to, at least one of water, ethanol, and isopropanol;
carrying out high-temperature carbonization, crushing and activation treatment on the obtained pre-carbide to obtain amorphous carbon with a median particle diameter D50 of 2-8 mu m, wherein the average sphericity is more than or equal to 0.6;
wherein the high-temperature carbonization treatment temperature can be 600-1400 ℃, and the heat preservation time can be 1-12 h; the activation treatment comprises at least one of physical activation and chemical activation, the temperature of the activation treatment can be 500-1000 ℃, and the activation time can be 1-12 h; wherein the physically activated gas includes, but is not limited to, at least one of steam, air, and carbon dioxide; the chemically activated chemical agent includes, but is not limited to, at least one of phosphoric acid, zinc chloride, potassium hydroxide, and sodium hydroxide.
The preparation method of amorphous carbon can prepare amorphous carbon with higher sphericity and more concentrated particle size distribution, and the high sphericity and the concentrated particle size distribution have positive effects on the subsequent nano silicon deposition process; compared with a carbon substrate with irregular morphology, the amorphous carbon with high sphericity has good fluidity and can be quickly and fully contacted with silane compound in the deposition process; the amorphous carbon having a concentrated particle size distribution can be more uniformly contacted with the silane compound than the carbon substrate having a wide particle size distribution, thereby allowing nano silicon to be more uniformly deposited in the amorphous carbon. Therefore, amorphous carbon with higher sphericity and more concentrated particle size distribution has a positive effect on improving the cell energy density and reducing the swelling effect.
In a preferred embodiment, the method of preparing the silicon carbon precursor includes, but is not limited to, vapor deposition, wherein the vapor deposition apparatus includes, but is not limited to, at least one of a chemical vapor deposition furnace and a fluidized bed.
In the vapor deposition process, the amorphous carbon with higher sphericity has good fluidity, the contact area of the amorphous carbon with more concentrated particle size distribution and the silane compound is more uniform, and the nano silicon particles can be more uniformly distributed in the amorphous carbon.
In a preferred embodiment, the vapor deposition temperature may be 400-800 ℃, and the typical but non-limiting temperature is 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the vapor deposition time may be 1-24 hours, and the typical but non-limiting time is 1 hour, 3 hours, 5 hours, 7 hours, 9 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours.
In the present invention, vapor deposition may be performed in an inert gas.
The vapor deposition method and the technological parameters thereof selected by the invention are more beneficial to improving the preparation effect of the silicon-carbon precursor, and can further ensure the preparation quality of the silicon-carbon precursor.
In a preferred embodiment, the silane compound includes, but is not limited to, at least one of monosilane, disilane, dimethylsilane, difluorosilane, tetrafluorosilane, trimethylfluorosilane, chlorosilane, methylchlorosilane, and dichlorosilane.
In the invention, the simple substance of silicon after pyrolysis treatment of the silane compound can be nano silicon particles, and the median diameter D50 of the nano silicon particles can be below 50 nm.
In a preferred embodiment, the method of passivating the silicon-carbon precursor includes, but is not limited to, a vapor phase passivation process, wherein the equipment of the vapor phase passivation process includes, but is not limited to, at least one of a chemical vapor deposition furnace and a fluidized bed.
In a preferred embodiment, the gas used for the vapor phase passivation process includes, but is not limited to, at least one of methane, ethane, propane, butane, ethylene, propylene, butene, 1, 3-butadiene, acetylene, methylacetylene, cyclopropane, and methyl chloride; the temperature of the vapor phase passivation treatment may be 400-800 ℃, and typical but non-limiting temperatures thereof are 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃; the time for the vapor phase passivation treatment may be 1 to 24 hours, and typical but non-limiting times are, for example, 1h, 3h, 5h, 7h, 9h, 12h, 14h, 16h, 18h, 20h, 22h, 24h.
In the invention, the gas phase passivation treatment also comprises a step of using air or oxygen for passivation treatment, wherein the treatment temperature can be 10-100 ℃, and the treatment time can be 1-24 h.
In the present invention, the passivation treatment may be performed in an inert gas, wherein the passivation layer after the passivation treatment may account for 0.1-5% of the mass of the anode material, for example, may be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, but is not limited thereto.
The passivation treatment method and the technological parameters thereof selected by the invention are more beneficial to further improving the treatment effect of the silicon-carbon precursor, thereby being capable of obtaining the anode material with good quality.
According to a third aspect of the present invention there is provided the use of a negative electrode material as defined in any one of the preceding claims in a lithium ion secondary battery.
The application of the negative electrode material provided by the invention can effectively improve the energy density of the lithium ion secondary battery and the first efficiency, and has an outstanding application effect.
In a preferred embodiment, the negative electrode material of the present invention and a secondary battery comprising metallic lithium as a counter electrode have a first reversible capacity of at least 1700 mA.h/g and a first efficiency of at least 92% when discharged to 0.005V at a constant current and then charged to a voltage of 1.5V at a constant current.
In a preferred embodiment, the negative electrode material of the present invention and the secondary battery comprising metallic lithium as a counter electrode have a first efficiency of 81% or more when charged at a constant current to a voltage of 0.8V.
In a preferred embodiment, the negative electrode material of the present invention and the secondary battery comprising metallic lithium as a counter electrode have a first efficiency of 66% or more when charged at a constant current to a voltage of 0.6V.
In the invention, a charge and discharge test is carried out on a cathode material and a secondary battery consisting of a metal lithium as a counter electrode, wherein lithium ions enter the cathode material for reaction in the discharge process, lithium ions are released from the cathode material for reaction in the charge process, the capacity Q of the charge process is differentiated from the voltage V of the cathode material, the obtained differential value dQ/dV is plotted with the voltage V, and the cathode electrode has a steamed bread peak in the voltage range of 0.4-0.5V.
The invention is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
Example 1
Negative electrode material (Si/C structure m The preparation method of m with the value of 1) comprises the following steps:
s1: 5kg of wheat starch and 2kg of phosphoric acid are mixed for carbonization at a low temperature of 200 ℃, and are added into a ball mill for ball milling for 12 hours, wherein the ball-to-material ratio is 1.6:1, ball milling at a rotational speed of 280rpm, thereby obtaining a pre-carbide with an average sphericity of 0.92;
s2: carbonizing the pre-carbide in a box-type atmosphere furnace at 1100 ℃ for 2 hours, and performing jet milling to obtain an amorphous carbon material, wherein physical and chemical index parameters are shown in table 1, a scanning electron microscope image 1000 times of the amorphous carbon material is shown in figure 1, a scanning electron microscope image 30000 times of the amorphous carbon material is shown in figure 2, and an XRD diffraction pattern of the amorphous carbon material is shown in figure 3;
s3: pyrolyzing amorphous carbon and monosilane in a CVD furnace at 550 ℃ for 3 hours to obtain a silicon-carbon precursor, then introducing methane for passivation treatment for 1 hour to obtain a negative electrode material, wherein physical and chemical index parameters are shown in table 2, a scanning electron microscope image of 1000 times of the negative electrode material is shown in fig. 4, and a scanning electron microscope image of 30000 times of the negative electrode material is shown in fig. 5;
wherein, the nano silicon accounts for 48.5wt% of the cathode material.
The ion milling section scanning electron microscope and the energy spectrum of the pole piece prepared from the anode material of the embodiment are shown in fig. 6, and the XRD diffraction pattern of the anode material of the embodiment is shown in fig. 7.
Example 2
The difference between this example and example 1 is that in step S1, this example replaces wheat starch with mung bean starch, and the rest of the steps and parameters thereof refer to example 1, resulting in amorphous carbon and negative electrode material (structure Si/C m M is 0.95), the physical and chemical index parameters of the amorphous carbon are shown in table 1, and the physical and chemical index parameters of the cathode material are shown in table 2.
Example 3
This example differs from example 1 in that in step S1, the present example replaces phosphoric acid with potassium hydroxide solution, and the rest of the steps and parameters thereof refer to example 1, resulting in amorphous carbon and a negative electrode material (structure Si/C m M is 1), the physical and chemical index parameters of the amorphous carbon are shown in table 1, and the physical and chemical index parameters of the cathode material are shown in table 2.
Example 4
Negative electrode material (Si/C structure m M is 0.92), comprising the following steps:
s1: mixing 5kg of sucrose with 50kg of pure water in an autoclave, controlling the pressure in the autoclave to be 1.5MPa, carbonizing at 200 ℃ for 5 hours, washing and drying to obtain a pre-carbide with the average sphericity of 0.95;
s2: uniformly mixing the pre-carbide with potassium hydroxide, carbonizing at 1300 ℃ for 2 hours in a box-type atmosphere furnace, and carrying out jet milling to obtain amorphous carbon, wherein the physical and chemical index parameters are shown in table 1;
s3: pyrolyzing amorphous carbon and monosilane in a CVD furnace at 500 ℃ for 4 hours to obtain a silicon-carbon precursor, and then introducing acetylene for passivation treatment for 1.5 hours to obtain a negative electrode material, wherein the physical and chemical index parameters are shown in Table 2;
wherein, the nano silicon accounts for 50 weight percent of the cathode material.
Example 5
This example differs from example 4 in that in step S1, sucrose was replaced with resorcinol, formaldehyde solution and ethylenediamine, pure water was replaced with ethanol, and the rest of the steps and parameters thereof were referred to example 4 to obtain amorphous carbon and a negative electrode material (structure Si/C m M is 0.9), the physical and chemical index parameters of the amorphous carbon are shown in table 1, and the cathode materialThe physicochemical index parameters of (2) are shown in Table.
Example 6
The difference between this example and example 4 is that in step S1, this example replaces sucrose with cellulose, and the rest of the steps and parameters thereof refer to example 4, resulting in amorphous carbon and a negative electrode material (structure Si/C m M is 0.9), the physical and chemical index parameters of the amorphous carbon are shown in table 1, and the physical and chemical index parameters of the cathode material are shown in table 2.
Example 7
Negative electrode material (Si/C structure m M is 1.05), comprising the following steps:
s1: uniformly mixing 4kg of tapioca starch with 20kg of zinc chloride aqueous solution (the concentration of the zinc chloride aqueous solution is 10 wt%) and granulating at 210 ℃ in a spray dryer, wherein the rotation speed of an atomizing disk of spray drying is 13500rpm, so as to obtain pre-carbide with the average sphericity of 0.88;
s2: carbonizing the pre-carbide in a box-type atmosphere furnace at 1200 ℃ for 4 hours, and performing jet milling to obtain amorphous carbon, wherein the physical and chemical index parameters are shown in table 1;
s3: carrying out pyrolysis on amorphous carbon and disilane in a CVD furnace at 600 ℃ for 2 hours to obtain a silicon-carbon precursor, and then introducing methane for passivation treatment for 1 hour to obtain a negative electrode material, wherein the physical and chemical index parameters are shown in Table 2;
wherein the nano silicon accounts for 47wt% of the cathode material.
Example 8
This example differs from example 7 in that in step S1, the present example replaces the aqueous zinc chloride solution with the aqueous phosphoric acid solution, and the rest of the steps and parameters thereof refer to example 7, resulting in amorphous carbon and a negative electrode material (structure Si/C m M is 1.05), the physical and chemical index parameters of the amorphous carbon are shown in table 1, and the physical and chemical index parameters of the cathode material are shown in table 2.
Example 9
The difference between this example and example 7 is that in step S1, this example replaces tapioca starch with maltose, and the rest of the steps and parameters thereof refer to example 7, resulting in amorphous carbon and negative electrode material (structure Si/C m M is 1.05), the physical and chemical index parameters of the amorphous carbon are shown in table 1, and the physical and chemical index parameters of the cathode material are shown in table 2.
Comparative example 1
The difference between this comparative example and example 1 is that in step S1, phosphoric acid was not added in this comparative example, and the rest of the steps and parameters thereof were referred to example 1 to obtain amorphous carbon, the physicochemical index parameters of which are shown in table 1; the negative electrode material was obtained, which had a sphericity of 0.85, a median particle diameter D50 of 10.58. Mu.m, a particle size distribution K90 of 1.58 and a specific surface area of 0.3 m/g.
Comparative example 2
The present comparative example is different from example 1 in that in step S1, the present comparative example replaces ball milling by stirring and heating under the condition of stirring at 200 c (rotation speed 400 rpm), and the rest of the steps and parameters thereof refer to example 1 to obtain amorphous carbon, the physicochemical index parameters of which are shown in table 1; the negative electrode material was obtained, which had a sphericity of 0.11, a median particle diameter D50 of 10.09 μm, a particle size distribution K90 of 1.84 and a specific surface area of 1.1 m/g.
Comparative example 3
The difference between this comparative example and example 1 is that in step S3, the present comparative example is not subjected to passivation treatment, and the rest of the steps and parameters thereof refer to example 1 to obtain amorphous carbon, and physical and chemical index parameters thereof are shown in table 1; the negative electrode material was obtained, which had a sphericity of 0.89, a median particle diameter D50 of 6.45 μm, a particle size distribution K90 of 1.17 and a specific surface area of 83.5 m/g.
Test example 1
The physicochemical index parameters of the amorphous carbon materials obtained in examples 1 to 9 and comparative examples 1 to 3 are shown in Table 1.
Testing the particle size (mum) range of the material by using a laser particle sizer BT-9300ST of Dandong;
measuring sphericity of the material by adopting BT-2800 particle size analysis of dynamic images of Dandongbaite;
carrying out phase analysis on the material by adopting an XRD diffractometer (Panalytical X' PERT PRO MPD of the Netherlands);
and testing the specific surface area (m/g) of the material by adopting a microscopic high-Bo JW-DX dynamic adsorption specific surface area instrument.
TABLE 1
As is clear from Table 1, in examples 1 to 9, the type of carbon source, different preparation methods, etc. all affect the physical and chemical indexes such as morphology, sphericity, granularity, specific surface area, etc. of amorphous carbon to some extent; the sphericity of amorphous carbon obtained in examples 1 to 9 and comparative examples 1 and 3 is high, and is mainly affected by the preparation method and the type of carbon source; in comparative example 1, the specific surface area of the amorphous carbon obtained was reduced without adding an additive for activation, and in comparative example 2, ball milling, solvothermal and spray drying treatments were not performed, the sphericity of amorphous carbon was significantly reduced, and fluidity was poor during the activation treatment, resulting in a reduction in the specific surface area.
Physical and chemical index parameters of the anode materials provided in examples 1 to 9 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2
As can be seen from table 2, in examples 1 to 9 and comparative examples 1 to 3, the different carbon sources and the different preparation methods have large differences in sphericity, granularity and specific surface area of the negative electrode material, wherein the differences in sphericity and granularity mainly come from the preparation and treatment of amorphous carbon, and the differences in specific surface area are determined by amorphous carbon, nano-silicon deposition process and passivation treatment; as is clear from comparative examples 1-2, the larger particle size of the negative electrode material is mainly that the smaller specific surface area of the amorphous carbon, resulting in more nano silicon being deposited on the surface of the amorphous carbon; the particle size distribution of comparative example 2 is the widest, mainly amorphous carbon, with lower sphericity and poor flowability, and more nano silicon is accumulated in small particles with poor flowability during nano silicon deposition; the cathode material of comparative example 3 has a larger specific surface area, and is mainly not subjected to passivation treatment, nano silicon deposition is a key factor for reducing the specific surface area of the cathode material, and the passivation treatment has a certain effect on reducing the specific surface area.
Test example 2
Lithium battery button cell test:
the anode materials obtained in examples 1 to 9 and comparative examples 1 to 3 were tested for the first reversible capacity and the first efficiency as follows:
the cathode material, the conductive carbon black and the binder are mixed according to the mass ratio of 94.5:1.5:4, mixing the materials in pure water, homogenizing, controlling the solid content to be 48wt%, coating the materials on a copper foil current collector, baking the materials for 8 hours at 100 ℃ in vacuum, and preparing a negative electrode plate through punching after compression molding;
the button half cell is assembled in a glove box filled with argon, a counter electrode is a metal lithium sheet, a diaphragm used is PE, and an electrolyte is LiPF of 1mol/L 6 EC/DMC (Vol 1:1);
the button cell is subjected to charge and discharge test, and the test flow is 0.2C DC to 0V,0.05C DC to 0V,0V CV 50 mu A,0.01C DC to 0V,0V CV 20 mu A and Rest 10min,0.2C CC to 2V;
the first reversible capacity and efficiency of the negative electrode material were measured, wherein the test device of the button cell was a LAND cell test system from blue electric electronics Inc. of Wuhan City.
Expansion ratio test of anode material S600:
the negative electrode materials obtained in examples 1-9 and comparative examples 1-3 were tested for the first reversible capacity according to the buckling test method described above, and then according to the calculation, a certain amount of the same graphite negative electrode was mixed, and the negative electrode materials were mixed to 600.+ -. 5 mA.h/g, abbreviated as S600;
mixing the materials, conductive carbon black and a binder (mass ratio of 92:2:6) according to S600, homogenizing, controlling the solid content to be 48%, coating the mixture on a current collector taking copper foil as a base material, then baking the mixture in vacuum at 90 ℃ for 8 hours, pressing the mixture by a rolling device to form the mixture, and slicing the mixture by a slicing device to prepare a negative electrode plate; detecting the thickness of the negative pole piece by using a ten-thousandth ruler, marking as T1, marking the thickness of a detection base material as T2, and recording data;
the button half cell is assembled in a glove box filled with argon, a counter electrode is a metal lithium sheet, a diaphragm used is PE material, and electrolyte is LiPF of 1mol/L 6 EC/DMC (Vol 1:1); the button cell is charged and discharged, test flow 0.1C DC to 0.005V,0.05C DC to 0.005V, 0.02C DC to 0.005V, rest 10min,0.1C CCto 1.5V,0.1C DC to 0.005V,0.05C DC to 0.005V, 0.02C DC to 0.005V; measuring the first reversible capacity and efficiency of the anode material;
disassembling the battery, and detecting the thickness of the negative electrode material obtained by disassembly and marking the thickness as T3; and (3) calculating according to a formula F= (T3-T1)/(T1-T2) to obtain first full-charge expansion data of the anode material, wherein F is the first full-charge expansion rate.
The button cell test equipment is LAND cell test system of blue electric electronic Co., ltd; the slicing equipment is Ke-jingjingsu MSK-T10 button half-cell slicing equipment; the ten-thousandth detection device is Mitutoyo 293-100-10; the rolling equipment is Ke-jingjingsu MSK-HRP-05 button half-cell slicing equipment.
The test results are shown in Table 3, the first charge and discharge curve of the lithium battery button cell of the negative electrode material of example 1 is shown in FIG. 8, and the first charge and discharge dQ/dV curve of the lithium battery button cell of the negative electrode material of example 1 is shown in FIG. 9.
TABLE 3 Table 3
As can be seen from Table 3, the anode materials prepared in examples 1-9 have high first reversible capacity and first efficiency, and in a lithium ion battery test system, the first reversible capacity can reach more than 1700 mA.h/g, and the first efficiency is more than 92%; the changes of the types of carbon sources and the preparation methods in examples 1-9 and comparative examples 1-3 can greatly influence the first efficiency and the first expansion rate of S600 of the anode material, amorphous carbon with larger specific surface area in examples 1-9 can enable nano silicon to be deposited in the pores of amorphous carbon, meanwhile, the direct contact between the nano silicon on the surface and electrolyte is isolated after passivation treatment, side reaction is reduced in the charging process, repeated formation of SEI is avoided, and accordingly the volume expansion change of the anode material in the lithium intercalation process can be reduced. In comparative example 1, the activation without adding an additive causes the amorphous carbon to have a smaller specific surface area, most of nano silicon is deposited on the surface of the amorphous carbon, the expansion is larger, the side reaction is more, and the first efficiency is greatly reduced. The amorphous carbon obtained in comparative example 2 has poor sphericity, the specific surface area is small due to poor flowability in the activation stage, nano silicon is unevenly deposited due to low sphericity and poor flowability in the nano silicon deposition stage, and more nano silicon is deposited on the surface of irregular small particles, so that the particle size distribution is wide, the expansion is large, and the electrochemical performance is deteriorated; the sphericity of comparative example 3 is high, the first reversible capacity is low and the S600 first expansion is large, because the silicon-carbon precursor is not subjected to passivation treatment, so that a large amount of nano silicon is deposited on the surface of amorphous carbon, and the nano silicon is in direct contact with electrolyte in the charge-discharge process, so that expansion is greatly increased, side reactions continuously occur to form an SEI film, and the first effect is reduced and the first reversible capacity is reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A negative electrode material characterized by comprising nano silicon particles and amorphous carbon;
the structure of the anode material is Si/C m Wherein m is more than or equal to 0.25 and less than or equal to 4;
the granularity distribution K90 of the anode material is between 0.9 and 1.4;
the average sphericity phi s of the anode material is between 0.6 and 1.0;
the median particle diameter D50 of the negative electrode material is 2-9 mu m.
2. The anode material according to claim 1, wherein the specific surface area of the anode material is between 0.5 and 10 m/g.
3. The negative electrode material according to claim 1, wherein the amorphous carbon has an average sphericity of 0.6-1.0;
the median diameter D50 of the amorphous carbon is 2-8 mu m;
the particle size distribution K90 of the amorphous carbon is between 0.8 and 1.8;
the specific surface area of the amorphous carbon is 500-3000 m/g.
4. The anode material according to claim 3, wherein the amorphous carbon has a pore volume of 0.5cm or more;
the pore structure of the amorphous carbon comprises at least two of micropores, mesopores and macropores;
the volume fraction of the micropores is 10-95%;
the volume fraction of the mesopores is 10-95%;
the volume fraction of macropores is less than 10%.
5. The anode material according to claim 1, wherein the nano-silicon particles are amorphous silicon;
the average particle size D50 of the nano silicon particles is less than 50nm;
the nano silicon particles account for 20-80 wt% of the cathode material.
6. A method for producing the anode material according to any one of claims 1 to 5, comprising the steps of:
(a) Preparing amorphous carbon with average sphericity more than or equal to 0.6;
(b) Pyrolyzing a silane compound in the pore structure of the amorphous carbon to deposit nano silicon particles in the pore structure of the amorphous carbon to obtain a silicon carbon precursor;
(c) And (3) passivating the silicon-carbon precursor in the step (b) to obtain the anode material.
7. The method for preparing amorphous carbon according to claim 6, characterized in that the method for preparing amorphous carbon comprises the steps of:
pre-carbonizing a carbon source material to obtain a pre-carbide;
the pre-carbide is carbonized, crushed and activated to obtain amorphous carbon;
the carbon source material comprises at least one of glucose, fructose, galactose, lactose, sucrose, maltose, rice starch, mung bean starch, wheat starch, tapioca starch, corn starch, cellulose and phenolic resin;
the pre-carbonization method comprises at least one of solvothermal reaction, low-temperature carbonization and spray drying;
the average sphericity of the pre-carbide is more than or equal to 0.6;
the activation treatment includes at least one of a physical activation method and a chemical activation method;
the gas used in the physical activation method comprises at least one of water vapor, air and carbon dioxide;
the chemical reagent of the chemical activation method comprises at least one of phosphoric acid, zinc chloride, potassium hydroxide and sodium hydroxide.
8. Use of the negative electrode material according to any one of claims 1 to 5 in a lithium ion secondary battery.
9. The use according to claim 8, wherein the first reversible capacity of the lithium ion secondary battery is equal to or more than 1700 mA-h/g and the first efficiency is equal to or more than 92% when discharging to 0.005V at a constant current and then charging to a voltage of 1.5V at a constant current.
10. The use according to claim 9, wherein the first efficiency of the lithium ion secondary battery is 81% or more when charged to a voltage of 0.8V at a constant current;
the first efficiency of the lithium ion secondary battery is 66% or more when charged to a voltage of 0.6V at a constant current.
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