CN114436238B - Preparation method of low-expansion silicon-carbon negative electrode material for lithium ion battery - Google Patents
Preparation method of low-expansion silicon-carbon negative electrode material for lithium ion battery Download PDFInfo
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 title claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 27
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- 238000000227 grinding Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
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- 238000005245 sintering Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010000 carbonizing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 102220043159 rs587780996 Human genes 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
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- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
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- 239000011300 coal pitch Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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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
- 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
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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
- H01M4/38—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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- 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
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- 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
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- 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
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- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a preparation method of a low-expansion silicon-carbon anode material for a lithium ion battery, which comprises the following steps: adding silicon powder, a binder, a pore-forming agent and a solvent into a sand mill according to a proportion, and grinding to obtain silicon slurry; drying the obtained silicon slurry into powder to obtain a silicon-carbon precursor; and finally, placing the obtained silicon-carbon precursor into a nitrogen atmosphere protection furnace for sintering, and crushing and screening to obtain the silicon-carbon anode material. By adopting a simple three-step method, the integrated preparation of pore-forming and coating is realized, through the method, the pore-forming agent is subjected to full thermal decomposition pore-forming on the surface of silicon powder, a preliminary pore skeleton is realized, asphalt flows on the surface of the pore skeleton to coat, an internal porous silicon-carbon material with uniform and compact surface coating is formed, the internal porous formed after carbonization can effectively buffer the volume expansion of silicon, and meanwhile, the surface compact coating layer can realize a low specific surface area, so that the interface is improved, and the capacity, the first efficiency and the power performance of the silicon-carbon cathode can be greatly improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a low-expansion silicon-carbon negative electrode material for a lithium ion battery.
Background
The lithium ion battery has the characteristics of high working voltage, high energy density, wide working temperature, long cycle life, no memory effect, environmental friendliness and the like, and is widely applied to the power battery fields of automobiles, electric bicycles and the like, the energy storage fields of electric power grids, industrial energy storage, household energy storage, communication energy storage and the like, and the 3C digital fields of smart phones, notebook computers, intelligent wearing equipment, mobile power supplies and the like.
The current commercial lithium battery cathode materials mainly comprise modified natural graphite and artificial graphite, and although the preparation technology is quite mature, the theoretical specific capacity of the lithium battery cathode materials is 372mAh/g, and the requirements of the market on a large-capacity lithium ion battery are difficult to meet, so that the development of a silicon-carbon cathode with higher gram capacity is currently increased. Although the capacity of the silicon carbon anode is high, the expansion is very large, and a volume expansion of about 300% can be achieved in the full-charge state. For example, chinese patent No. 109659551A discloses a preparation method of a silicon cathode material for a low-expansion lithium ion battery, which comprises the steps of dispersing nano silicon powder in ultrapure water to prepare silicon slurry; adding benzenediol, formaldehyde and sodium carbonate into the silicon slurry to prepare silica sol; forming silica sol to obtain silica gel; aging and carbonizing the silica gel to obtain carbonized material; crushing and grading the carbonized material to obtain a silicon-carbon composite material A; dipping and surface coating the silicon-carbon composite material A by adopting mesophase pitch to obtain a coating material B; and (3) carbonizing and sieving the coating material B to obtain the silicon anode material for the low-expansion lithium ion battery. The method has complex steps, and high energy consumption due to heat treatment in multiple steps, and is not beneficial to industrialization.
Therefore, there is a need for improvements in the existing methods for preparing silicon negative electrode materials for low expansion lithium ion batteries.
Disclosure of Invention
In view of the above, the invention aims at overcoming the defects in the prior art, and mainly aims to provide a preparation method of a low-expansion silicon-carbon negative electrode material for a lithium ion battery, which has the advantages of simple process and low energy consumption, thereby further reducing the cost, being convenient for popularization and application and being beneficial to industrialization.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the low-expansion silicon-carbon negative electrode material for the lithium ion battery comprises the following steps of:
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1: (0.05-0.5): (0.05-0.1): adding the silicon slurry into a sand mill according to the mass ratio of (0.5-2.0) for grinding for 1-5h, wherein the grinding speed is 500-2500r/min, so as to obtain silicon slurry;
(2) Granulating: drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 150-300 ℃, the air outlet temperature is 100-150 ℃, and the rotation degree of a constant flow pump is 50-100r/min, so as to obtain a silicon carbon precursor;
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, raising the temperature to 1100-1500 ℃ at a heating rate of 2-25 ℃/min, preserving the temperature for 6-12 hours, and crushing and screening to obtain the silicon-carbon anode material.
As a preferable scheme, the silicon powder d50=20-100 nm in the step (1) has a spherical shape.
As a preferable scheme, the binder in the step (1) is one or a mixture of coal-based asphalt and oil-based asphalt, and the softening point of the binder is 50-200 ℃.
As a preferable scheme, the pore-forming agent in the step (1) is one or more than two of ammonium bicarbonate, ammonium carbonate, ammonium oxalate, ammonium nitrate, ammonium phosphate and ammonium hydrogen phosphate.
As a preferable mode, the solvent in the step (1) is one or more of benzene, toluene and xylene.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and in particular, the technical scheme can be as follows:
according to the invention, a simple three-step method is adopted to realize integrated preparation of pore-forming and coating, by the method, pore-forming agent is subjected to full thermal decomposition on the surface of silicon powder to form a preliminary pore skeleton, asphalt flows on the surface of the pore skeleton to coat, so that an internal porous and uniformly-compactly-coated silicon-carbon material is formed, the internal porous formed after carbonization can effectively buffer the volume expansion of silicon, and meanwhile, the compactly-coated coating layer on the surface can realize low specific surface area, so that the interface is improved, and the capacity, the first efficiency and the power performance of a silicon-carbon anode can be greatly improved. In addition, the invention has simple process, simple operation and lower energy consumption, thereby further reducing the cost, being convenient for popularization and application and being beneficial to industrialization.
In order to more clearly illustrate the features and effects of the present invention, the present invention will be described in detail with reference to specific examples.
Detailed Description
The invention discloses a preparation method of a low-expansion silicon-carbon anode material for a lithium ion battery, which comprises the following steps:
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1: (0.05-0.5): (0.05-0.1): adding the silicon slurry into a sand mill according to the mass ratio of (0.5-2.0) for grinding for 1-5h, wherein the grinding speed is 500-2500r/min, so as to obtain silicon slurry; silicon powder D50=20-100 nm, and the morphology of the silicon powder is spherical; the binder is one or a mixture of coal-series asphalt and oil-series asphalt, and the softening point of the binder is 50-200 ℃; the pore-forming agent is one or more than two of ammonium bicarbonate, ammonium carbonate, ammonium oxalate, ammonium nitrate, ammonium phosphate and ammonium hydrogen phosphate; the solvent is one or more of benzene, toluene and xylene.
(2) Granulating: and (3) drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 150-300 ℃, the air outlet temperature is 100-150 ℃, and the rotation degree of a constant flow pump is 50-100r/min, so as to obtain the silicon carbon precursor.
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, raising the temperature to 1100-1500 ℃ at a heating rate of 2-25 ℃/min, preserving the temperature for 6-12 hours, and crushing and screening to obtain the silicon-carbon anode material.
The invention is described in further detail below in a number of examples:
example 1
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1:0.05:0.05: grinding for 1h by adding a sand mill with the mass ratio of 0.5 and the grinding speed of 500r/min to obtain silicon slurry; silicon powder D50=20-100 nm, and the morphology of the silicon powder is spherical; the binder is coal pitch with a softening point of 50-200 ℃; the pore-forming agent is ammonium bicarbonate; the solvent is benzene.
(2) Granulating: drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 200 ℃, the air outlet temperature is 120 ℃, and the rotation degree of a constant flow pump is 80r/min, so as to obtain a silicon-carbon precursor;
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, heating to 1200 ℃ at a heating rate of 20 ℃/min, preserving heat for 8 hours, and crushing and screening to obtain the silicon-carbon anode material.
Example 2
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1:0.5:0.1:2.0, adding into a sand mill for grinding for 5 hours, wherein the grinding speed is 2500r/min, and obtaining silicon slurry; silicon powder D50=20-100 nm, and the morphology of the silicon powder is spherical; the binder is oil asphalt, and the softening point of the binder is 50-200 ℃; the pore-forming agent is ammonium carbonate; the solvent is toluene.
(2) Granulating: and (3) drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 180 ℃, the air outlet temperature is 140 ℃, and the rotation degree of a constant flow pump is 55r/min, so as to obtain the silicon-carbon precursor.
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, heating to 1250 ℃ at a heating rate of 15 ℃/min, preserving heat for 10 hours, and crushing and screening to obtain the silicon-carbon anode material.
Example 3
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1:0.1:0.08:1, adding the mixture into a sand mill for grinding for 3 hours, wherein the grinding speed is 1500r/min, and obtaining silicon slurry; silicon powder D50=20-100 nm, and the morphology of the silicon powder is spherical; the binder is a mixture of coal-series asphalt and oil-series asphalt, and the softening point of the binder is 50-200 ℃; the pore-forming agent is ammonium oxalate; the solvent is xylene.
(2) Granulating: and (3) drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 150 ℃, the air outlet temperature is 100 ℃, and the rotation degree of a constant flow pump is 50r/min, so as to obtain the silicon-carbon precursor.
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, heating to 1200 ℃ at a heating rate of 8 ℃/min, preserving heat for 8 hours, crushing and screening to obtain the silicon-carbon anode material.
Example 4
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1:0.2:0.09: grinding for 3 hours by adding a sand mill according to the mass ratio of 1, wherein the grinding speed is 500-2500r/min, and obtaining silicon slurry; silicon powder D50=20-100 nm, and the morphology of the silicon powder is spherical; the binder is coal pitch with a softening point of 50-200 ℃; the pore-forming agent is ammonium nitrate; the solvent is a mixture of benzene and toluene.
(2) Granulating: and (3) drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 300 ℃, the air outlet temperature is 150 ℃, and the rotation degree of a constant flow pump is 100r/min, so as to obtain the silicon-carbon precursor.
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, heating to 1400 ℃ at a heating rate of 15 ℃/min, preserving heat for 10 hours, crushing and screening to obtain the silicon-carbon anode material.
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1:0.2:0.09:1, adding the mixture into a sand mill for grinding for 3 hours, wherein the grinding speed is 12500r/min, and obtaining silicon slurry; silicon powder D50=20-100 nm, and the morphology of the silicon powder is spherical; the binder is coal pitch with a softening point of 50-200 ℃; the pore-forming agent is ammonium phosphate; the solvent is benzene.
(2) Granulating: and (3) drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 200 ℃, the air outlet temperature is 120 ℃, and the rotation degree of a constant flow pump is 80r/min, so as to obtain the silicon-carbon precursor.
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, heating to 1100 ℃ at a heating rate of 2 ℃/min, preserving heat for 6 hours, and crushing and screening to obtain the silicon-carbon anode material.
Example 6
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1:0.2:0.09:1, adding the mixture into a sand mill for grinding for 3 hours, wherein the grinding speed is 1500r/min, and obtaining silicon slurry; silicon powder D50=20-100 nm, and the morphology of the silicon powder is spherical; the binder is coal pitch with a softening point of 50-200 ℃; the pore-forming agent is ammonium hydrogen phosphate; the solvent is a mixture of benzene and toluene.
(2) Granulating: and (3) drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 300 ℃, the air outlet temperature is 120 ℃, and the rotation degree of a constant flow pump is 80r/min, so as to obtain the silicon-carbon precursor.
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, heating to 1500 ℃ at a heating rate of 25 ℃/min, preserving heat for 12 hours, and crushing and screening to obtain the silicon-carbon anode material.
Performance testing
The silicon-carbon negative electrode materials prepared in the above examples were coated with the silicon-carbon negative electrode materials prepared in comparative example 1, in which no pore-forming agent was added, and the other steps were performed to test the properties of the silicon-carbon negative electrode materials prepared in comparative example 1, which were the same as those of the above examples, as shown in table 1 below.
TABLE 1
As can be seen from Table 1, the prepared silicon-carbon negative electrode material has excellent capacity performance, cycle performance, initial charge and discharge efficiency, low expansion performance and rate capability. The dual-carbon layer structure formed by the pore-forming agent and the binder plays a very key role, so that the pore-forming buffer expansion is realized, the low specific surface area is realized, the interface impedance is reduced, and the performances in all aspects are improved.
Test method
(1) The specific surface area of the material was measured using a Micromeritics TriStar II 3020 specific surface area meter from american microphone instruments;
(2) The cathode materials of the above examples and comparative examples were tested by a half-cell test method, wherein the cathode materials were prepared by mixing SBR (solid content: 50%) with CMC (CMC) with Super-p=95.5:2:1.5:1 (weight ratio), adding a proper amount of deionized water to prepare a slurry, coating the slurry on a copper foil, and drying in a vacuum drying oven for 12 hours to prepare a cathode sheet, wherein the electrolyte was 1M, liPF 6 Ec+dec+dmc=1:1:1, polypropylene microporous membrane as separator and counter electrode as lithium sheet, assembled into battery. Constant-current charge-discharge experiment is carried out in a LAND battery test system, the charge-discharge voltage is limited to 0.01-3.0V, a computer-controlled charge-discharge cabinet is used for collecting and controlling data, and a pole piece under full charge is measuredAnd (5) rebound.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical principles of the present invention are still within the scope of the technical solutions of the present invention.
Claims (2)
1. A preparation method of a low-expansion silicon-carbon negative electrode material for a lithium ion battery is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Mixing: silica powder, a binder, a pore-forming agent and a solvent are mixed according to the following ratio of 1: (0.05-0.5): (0.05-0.1): adding the silicon slurry into a sand mill according to the mass ratio of (0.5-2.0) for grinding for 1-5h, wherein the grinding speed is 500-2500r/min, so as to obtain silicon slurry; wherein the binder is one or a mixture of coal-series asphalt and oil-series asphalt, and the softening point of the binder is 50-200 ℃; the pore-forming agent is one or more than two of ammonium bicarbonate, ammonium carbonate, ammonium oxalate, ammonium nitrate, ammonium phosphate and ammonium hydrogen phosphate; the solvent is one or more of benzene, toluene and xylene;
(2) Granulating: drying the silicon slurry obtained in the step (1) into powder by a spray dryer, wherein the air inlet temperature of spray drying is 150-300 ℃, the air outlet temperature is 100-150 ℃, and the rotating speed of a constant flow pump is 50-100r/min, so as to obtain a silicon-carbon precursor;
(3) Carbonizing: and (3) placing the silicon-carbon precursor obtained in the step (2) into a nitrogen atmosphere protection furnace for sintering, raising the temperature to 1100-1500 ℃ at a heating rate of 2-25 ℃/min, preserving the temperature for 6-12 hours, and crushing and screening to obtain the silicon-carbon anode material.
2. The method for preparing the low-expansion silicon-carbon negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the silicon powder D50=20-100 nm in the step (1) is spherical in shape.
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