CN114583122A - Carbon-silicon negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Carbon-silicon negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN114583122A CN114583122A CN202210114326.1A CN202210114326A CN114583122A CN 114583122 A CN114583122 A CN 114583122A CN 202210114326 A CN202210114326 A CN 202210114326A CN 114583122 A CN114583122 A CN 114583122A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 59
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- 229920003002 synthetic resin Polymers 0.000 claims description 23
- 239000010405 anode material Substances 0.000 claims description 17
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- 238000000034 method Methods 0.000 claims description 12
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 2
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
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- 238000007599 discharging Methods 0.000 claims description 2
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- 239000007849 furan resin Substances 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
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- 238000010438 heat treatment Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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 carbon-silicon negative electrode material, a preparation method thereof and a lithium ion battery. The preparation method comprises the steps of mixing loose nano-silicon with a carbohydrate compound, then carbonizing, mixing a carbonized product with a high molecular resin solution and a resin curing agent, drying and curing, and performing high-temperature treatment in a reducing atmosphere to obtain the loose nano-carbon negative electrode material; wherein the mass ratio of the high molecular resin, the resin curing agent, the loose nano silicon and the carbohydrate is 0.15-0.18: 0.04-0.05: 1-1.5: 3.5-4. The invention further provides the carbon-silicon negative electrode material obtained by the preparation method and a lithium ion battery prepared from the carbon-silicon negative electrode material. The lithium ion battery prepared from the carbon-silicon negative electrode material has high gram capacity exertion and first efficiency and excellent electrochemical cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a carbon-silicon cathode material, a preparation method thereof and a lithium ion battery.
Background
Since the end of the 20 th century, lithium ion batteries have been widely used in the fields of smart phones, digital cameras, notebook computers, electric vehicles, and the like due to their advantages of high energy density, no memory effect, long life cycle, and environmental friendliness. However, the current commercial graphite cathode is difficult to meet the current requirement of high energy density cell due to the limit of theoretical capacity, so that a high-capacity cathode material needs to be found. The theoretical lithium intercalation capacity of the graphite cathode is 372mAh g-1The theoretical storage lithium capacity of the silicon material is 4200mAh/g, and the lithium desorption voltage platform is low, so that the silicon material gradually becomes an ideal negative electrode material research hotspot. However, its application in lithium ion batteries is limited due to poor cycle stability and rate performance. At present, the most of the modification of the silicon-carbon graphite negative electrode is that the coating of asphalt can cause mutual adhesion among coating particles, the coating is insufficient due to too small dosage, the material is easy to expand in the heating process, the electrical property of the material is influenced, and the pure direct mixing of the nano silicon powder and the resin-based material can still reduce the overall electrical property of the battery cell due to the poor electrical conductivity of silicon.
Disclosure of Invention
In order to solve the problems, the invention provides a carbon-silicon negative electrode material, a preparation method thereof and a lithium ion battery. The preparation method of the carbon-silicon cathode material provided by the invention is beneficial to increasing the particle size of the material and obtaining the battery cathode material with excellent electrochemical cycle performance.
In order to achieve the above object, the present invention provides a method for preparing a carbon-silicon anode material, comprising: mixing loose nano silicon with a carbohydrate compound, carbonizing to obtain a carbonized product, mixing the carbonized product with high molecular resin and a resin curing agent, drying and curing, and treating at the high temperature of 700-; wherein the mass ratio of the high molecular resin, the resin curing agent, the loose nano silicon and the carbohydrate is 0.15-0.18: 0.04-0.05: 1-1.5: 3.5-4.
In the preparation method, the carbohydrate compound can enter the pores of the loose nano-silicon in the process of mixing the loose nano-silicon with the carbohydrate compound, and the carbohydrate compound is decomposed to form amorphous carbon deposited on the surfaces of the inner wall and the outer wall of the loose nano-silicon through high-temperature carbonization, so that the surface exposure of the loose nano-silicon can be avoided, and the overall conductivity of the loose nano-silicon can be improved. Compared with the preparation of the anode material by using untreated loose nano-silicon, the anode material prepared by using the loose nano-silicon treated by the carbohydrate compound provided by the invention has the advantages that the initial capacity and the initial coulombic efficiency are obviously improved, and the amount of lithium ions consumed in the SEI film formation process is less.
In the preparation method, the particle size of the loose nano-silicon is generally 1 μm-10 μm, and the specific surface area of the loose nano-silicon is generally 10.25m2/g-25.32m2(iv) g. In the specific embodiment of the invention, the loose nano silicon can be formed by etching the nano silicon alloy by using acid, and the specific surface area of the nano silicon can be increased and the contact area of the nano silicon and the carbohydrate compound can be increased by the acid etching process.
In the above preparation method, the nano silicon alloy includes one or a combination of two or more of aluminum silicon alloy, magnesium silicon alloy, zinc aluminum silicon alloy and the like. The grain diameter of the nano silicon alloy is generally 3-15 μm.
During the etching of the nano-silicon alloy, the acid is generally in excess relative to the nano-silicon alloy. The acid used in the etching process generally includes one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and the like. Wherein, hydrochloric acid, sulfuric acid and nitric acid are generally in the form of dilute solution.
In the above-mentioned production method, the saccharide compound may include one or a combination of two or more of starch, glucose, sucrose, cellulose and the like.
In the above preparation method, the carbonization temperature is generally controlled to 80 ℃ to 100 ℃. The carbonization process can enable the carbohydrate to permeate into the nano silicon after acid etching, so that the nano silicon forms high-activity points, and the wettability between the nano silicon and the high polymer resin is improved.
In the preparation method, the carbonized product of the loose nano silicon and the carbohydrate is mixed with the polymer resin for curing, and the cured polymer resin can play a role of framework support to prevent the occurrence of fusion bonding blocks in the high-temperature treatment process (700-1000 ℃ treatment for 2-5 h); meanwhile, the three-dimensional loose nano silicon structure formed after the resin is cured can also inhibit the large-volume expansion of the material during lithium intercalation and lithium deintercalation. Through the curing process, the resin-based nano silicon material with an integrated structure can be obtained. Wherein the curing temperature may be 30 ℃ to 60 ℃.
In the above production method, the polymer resin may include a thermoplastic resin. The number average molecular weight of the polymeric resin may be 60000 to 90000. The polymer resin may specifically include one or a combination of two or more of furan resin, phenol resin, urea resin, epoxy resin, polyoxymethylene methyl acrylate resin, and the like.
In the above-mentioned production method, the polymer resin is generally added in the form of a solution. The solvent of the polymer resin solution may include an organic solvent, and for example, the organic solvent may include one or a combination of two or more of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, n-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, n-pentanol, 2-hexanol, and the like. In some embodiments, in the polymer resin solution, the mass ratio of the polymer resin to the organic solvent may be controlled to be 0.15 to 0.18: 10-12.
In the above preparation method, the resin-based curing agent may include one or a combination of two or more of hexamethylenetetramine, diethylaminopropylamine, trimethylhexamethylenediamine, dihexyltriamine, and the like.
In the preparation method, the macromolecular resin is adopted as the coating material, so that the material has better fluidity at low temperature, and the coating surface can also penetrate into the gaps of the loose nano silicon, thereby improving the tap density and the contact conductivity of the material. The polymer resin can play a role of skeleton support after being cured, can also enable a carbon structure formed after high-temperature treatment to have stronger corrosion resistance to electrolyte, and can increase the carbon layer spacing (the carbon layer spacing can be specifically the distance in the d002 direction in atomic arrangement, in some specific embodiments, the addition of the polymer resin can improve the carbon layer spacing in the d002 direction from 0.2655nm to 0.3396nm) and improve the lithium ion migration capacity. The holes and gaps formed after the loose nano silicon particles and the high polymer resin are carbonized in the high-temperature treatment process can buffer the volume expansion effect, and the overall performance of the material is ensured.
In the preparation method, the temperature of the high-temperature treatment is generally controlled to be 700-1000 ℃, and the time of the high-temperature treatment is generally controlled to be 2-5 h. In some embodiments, the high temperature treatment process comprises heating the cured product to 700 ℃ to 1000 ℃ at a rate of 10 ℃/min to 20 ℃/min in a reducing atmosphere, and holding for 2h to 5 h.
In the above production method, the reducing atmosphere includes a reducing gas; the reducing gas preferably comprises hydrogen; preferably, the reducing atmosphere further comprises an inert gas; the inert gas preferably comprises argon.
In the preparation method, the preparation method further comprises the operations of crushing, sieving and adjusting the sphericity after high-temperature treatment. Preferably, the sphericity is generally adjusted to 80% to 90%.
According to a specific embodiment of the present invention, the method for preparing the carbon-silicon anode material may include:
1. soaking the nano silicon alloy in excessive acid solution for etching to obtain loose nano silicon;
2. the loose nano silicon and carbohydrate such as starch are mixed according to the weight ratio of 1-1.5: 3.5-4, and carbonizing at 80-100 ℃ to obtain a carbonized product;
3. according to the following polymer resin: resin curing agent: loose nano silicon is 0.15-0.18: 0.04-0.05: 1-1.5, mixing the carbonized product with a resin curing agent and a polymer resin solution (the mass ratio of the polymer resin to the solvent is preferably 0.15-0.18: 10-12), drying and curing to obtain a cured product;
4. and heating the cured product to 700-1000 ℃ at the speed of 10-20 ℃/min in a reducing atmosphere, carrying out high-temperature treatment for 2-5h, crushing, sieving, and adjusting the sphericity to 80-90% to obtain the carbon-silicon negative electrode material.
The invention also provides a carbon-silicon negative electrode material which is prepared by the preparation method. Preferably, the particle size of the carbon silicon anode material is generally 1 μm to 10 μm, for example 2 μm to 7 μm. The carbon-silicon cathode material has the characteristics of high capacity and high multiplying power.
The invention further provides a lithium ion battery, and the raw material of the lithium ion battery comprises the carbon-silicon negative electrode material. Preferably, the gram capacity of the lithium ion battery is over 760mAh/g, the first charging and discharging efficiency of the lithium ion battery is over 86%, the lithium ion battery is charged and discharged for 50 times at 0.02C/0.2C, and the capacity retention rate of the lithium ion battery is over 88%.
The invention has the beneficial effects that:
the preparation method provided by the invention has the advantages of rich raw material sources and simple preparation process, and the prepared silicon-carbon anode material has a loose structure, higher tap density, higher conductivity, higher gram capacity exertion and first efficiency, excellent electrochemical cycle performance and suitability for industrialization.
Drawings
Fig. 1 is an SEM photograph of the carbon silicon anode material of example 1.
A in fig. 2 is an enlarged view of a position a in fig. 1, and B in fig. 2 is an enlarged view of a position B in fig. 1.
Fig. 3 is an SEM photograph of the carbon silicon anode material of example 2.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a carbon-silicon anode material, and a preparation method thereof comprises the following steps:
1. weighing 1g of nano silicon-aluminum alloy powder, adding the nano silicon-aluminum alloy powder into 20g of dilute hydrochloric acid solution with the concentration of 2mol/L, and stirring the solution sufficiently to react until no bubbles are generated, thereby obtaining loose nano silicon;
2. mixing the loose nano silicon and starch water solution according to the weight ratio of 1: 3.5 (based on the mass of the starch), and then drying and carbonizing the mixture in an environment of 100 ℃ to obtain carbonized loose nano silicon powder;
3. adding the carbonized loose nano silicon powder into an ethanol solution of phenolic resin (ethanol is the only solvent) for carrying out ultrasonic treatment for 1h, uniformly mixing, then dropwise adding diethylaminopropylamine, placing in an oven at 60 ℃ to complete curing, wherein the mass ratio of the loose nano silicon powder to the ethanol to the phenolic resin to the diethylaminopropylamine is 1: 10: 0.15: 0.04 of;
4. heating the cured product obtained in the step (3) to 900 ℃ at the speed of 10 ℃/min under the protection of argon gas, preserving the heat for 3h, and naturally cooling to room temperature;
5. and (4) crushing and sieving the product obtained in the step (4), and adjusting the sphericity to 90% by using a vibration mill to obtain the silicon-carbon negative electrode material with a loose structure.
Example 2
The embodiment provides a carbon-silicon anode material, and a preparation method thereof comprises the following steps:
1. weighing 1g of nano silicon-aluminum alloy powder, adding the nano silicon-aluminum alloy powder into 20g of dilute hydrochloric acid solution with the concentration of 2mol/L, and stirring the solution sufficiently to react until no bubbles are generated, thereby obtaining loose nano silicon;
2. mixing the loose nano silicon with glucose aqueous solution according to the weight ratio of 1: 3.5 (by mass of glucose), drying and carbonizing in an environment of 100 ℃ after mixing and stirring for 2 hours to obtain carbonized loose nano silicon powder;
3. adding the carbonized loose nano silicon powder into an ethanol solution (ethanol is the only solvent) of phenolic resin for ultrasonic treatment for 1h, uniformly mixing, dropwise adding dihexyl triamine, and putting into an oven at 60 ℃ to finish curing, wherein the mass ratio of the loose nano silicon powder to the ethanol to the phenolic resin to the dihexyl triamine is 1: 10: 0.15: 0.04;
4. heating the cured product obtained in the step (3) to 900 ℃ at the speed of 10 ℃/min under the protection of argon gas, preserving the heat for 3h, and naturally cooling to room temperature;
5. and (4) crushing and sieving the product obtained in the step (4), and adjusting the sphericity to 90% by using a vibration mill to obtain the silicon-carbon negative electrode material with a loose structure.
Comparative example 1
The comparative example provides a carbon-silicon anode material, and no saccharide compound is added in the preparation process of the carbon-silicon anode material, and specifically, the preparation method of the carbon-silicon anode material comprises the following steps:
1. weighing 1g of nano silicon-aluminum alloy powder, adding the nano silicon-aluminum alloy powder into 20g of dilute hydrochloric acid solution with the concentration of 2mol/L, and stirring the solution sufficiently to react until no bubbles are generated, thereby obtaining loose nano silicon;
2. adding the loose nano silicon powder into an ethanol solution of phenolic resin (ethanol is the only solvent) for carrying out ultrasonic treatment for 1 hour, uniformly mixing, then dropwise adding dihexyl triamine, and putting into an oven at 60 ℃ to complete curing, wherein the mass ratio of the loose nano silicon powder to the ethanol to the phenolic resin to the dihexyl triamine is 1: 10: 0.15: 0.04;
3. heating the cured product obtained in the step 2 to 900 ℃ at the speed of 10 ℃/min under the protection of argon inert gas, preserving the heat for 3h, and naturally cooling to room temperature;
4. and (4) crushing and sieving the product obtained in the step (3), and adjusting the sphericity to 90% by using a vibration mill to obtain the silicon-carbon negative electrode material.
Comparative example 2
The comparative example provides a carbon-silicon negative electrode material, and no saccharide compound is added in the preparation process, and specifically, the preparation method of the carbon-silicon negative electrode material comprises the following steps:
1. weighing 1g of nano silicon-aluminum alloy powder, adding the nano silicon-aluminum alloy powder into 20g of dilute hydrochloric acid solution with the concentration of 2mol/L, and stirring the solution sufficiently to react until no bubbles are generated, thereby obtaining loose nano silicon;
2. adding loose nano silicon powder into a phenolic resin solution taking ethanol as a solvent, carrying out ultrasonic treatment for 1h, uniformly mixing, then dropwise adding dihexyl triamine, and putting into an oven at 60 ℃ to finish curing, wherein the mass ratio of the loose nano silicon powder to the ethanol to the phenolic resin to the dihexyl triamine is 1: 10: 0.15: 0.04;
3. heating the cured product obtained in the step 2 to 1000 ℃ at the speed of 10 ℃/min under the protection of argon gas, preserving the heat for 3h, and naturally cooling to room temperature;
4. and (4) crushing and sieving the product obtained in the step (3), and adjusting the sphericity to 90% by using a vibration mill to obtain the silicon-carbon negative electrode material.
Test example 1
The performance of the loose silicon-carbon negative electrode materials of example 1, example 2, comparative example 1 and comparative example 2 as negative electrode materials of lithium ion batteries was tested. Meanwhile, the particle size of the loose silicon-carbon anode material is tested by a malvern laser particle sizer, and the results are summarized in table 1.
Mixing the loose silicon carbon negative electrode material with conductive carbon black, CMC and SBR according to the proportion of 96.4: 0.6: 1.3: 1.7, mixing to form a negative electrode material; the electrolyte is LiPF with the mass ratio of 1:1:16The film is a coated ceramic polyethylene film, the negative electrode material is used as a positive electrode, a metal lithium sheet is used as a negative electrode to prepare a half cell, the half cell is tested at 0.2C/0.2C for the first charge-discharge efficiency (first effect) and gram capacity at the room temperature of 25 ℃, and the film is tested at the room temperature of 25 ℃ for 50 times for charge-discharge capacity retention rate and other performances by 1C/1C charge-discharge at the room temperature of 25 ℃, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, the addition of the saccharide compound during the preparation of the carbon-silicon negative electrode material is beneficial to increase the particle size of the negative electrode material, and is beneficial to improve the first charge-discharge efficiency, gram capacity exertion, charge-discharge capacity retention rate, tap density and conductivity of the lithium ion battery prepared from the negative electrode material.
Fig. 1 is an SEM photograph of a carbon silicon negative electrode material of example 1, where a in fig. 2 is an enlarged view of a position a in fig. 1, and B in fig. 2 is an enlarged view of a position B in fig. 1. Fig. 3 is an SEM photograph of the carbon silicon anode material of example 2. As can be seen from fig. 1,2 and 3, the carbon silicon anode material prepared in example 1 has a loose porous structure.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be appreciated by those skilled in the art that the present invention is not limited by the embodiments described above, which are presented in the description to illustrate the principles of the invention. It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the protective scope of the present invention.
Claims (10)
1. A preparation method of a carbon-silicon anode material comprises the following steps: mixing loose nano silicon and a carbohydrate and then carbonizing to obtain a carbonized product, then mixing the carbonized product with high molecular resin and a resin curing agent, drying and curing, and performing high-temperature treatment in a reducing atmosphere to obtain the carbon-silicon negative electrode material;
wherein the mass ratio of the high molecular resin, the resin curing agent, the loose nano silicon and the carbohydrate is 0.15-0.18: 0.04-0.05: 1-1.5: 3.5-4.
2. The preparation method of claim 1, wherein the particle size of the loose nano-silicon is 1 μm to 10 μm, and the specific surface area of the loose nano-silicon is 10.25m2/g-25.32m2/g；
Preferably, the loose nano-silicon is formed by acid etching of a nano-silicon alloy;
preferably, the nano silicon alloy comprises one or a combination of more than two of aluminum-silicon alloy, magnesium-silicon alloy and zinc-aluminum-silicon alloy; the grain diameter of the nano silicon alloy is 3-15 mu m;
preferably, the acid used for etching the nano silicon alloy comprises one or a combination of more than two of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
3. The production method according to claim 1 or 2, wherein the sugar compound includes one or a combination of two or more of starch, glucose, sucrose, and cellulose.
4. The production method according to any one of claims 1 to 3, wherein the polymer resin includes a thermoplastic resin;
preferably, the number average molecular weight of the polymer resin is 60000 to 90000;
preferably, the polymer resin comprises one or a combination of more than two of furan resin, phenolic resin, urea resin, epoxy resin and polyformaldehyde methyl acrylate resin;
preferably, the polymer resin is added in the form of a solution, and the solvent of the polymer resin solution includes an organic solvent, and more preferably, the organic solvent includes one or a combination of two or more of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, n-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, n-pentanol, and 2-hexanol;
preferably, in the polymer resin solution, the mass ratio of the polymer resin to the organic solvent is 0.15-0.18: 10-12.
5. The method according to claim 4, wherein the resin-based curing agent comprises one or a combination of two or more of hexamethylenetetramine, diethylaminopropylamine, trimethylhexamethylenediamine, and dihexyltriamine.
6. The production method according to any one of claims 1 to 5, wherein the temperature of the carbonization is 80 to 100 ℃; the curing temperature is 30-60 ℃.
7. The preparation method according to any one of claims 1 to 6, wherein the temperature of the high temperature treatment is 700-1000 ℃, and the time of the high temperature treatment is 2-5 h;
preferably, the reducing atmosphere comprises a reducing gas; the reducing gas preferably comprises hydrogen;
more preferably, the reducing atmosphere further comprises an inert gas; the inert gas preferably comprises argon.
8. The production method according to any one of claims 1 to 7, wherein the production method further comprises an operation of crushing, sieving, and adjusting sphericity after the high-temperature treatment;
preferably, the sphericity is adjusted to 80-90%.
9. A carbon silicon negative electrode material obtained by the production method according to any one of claims 1 to 8;
preferably, the carbon-silicon negative electrode material has a particle size of 1 μm to 10 μm, more preferably 2 μm to 7 μm.
10. A lithium ion battery, the raw material of which comprises the carbon-silicon negative electrode material of claim 9;
preferably, the gram capacity exertion of the lithium ion battery is more than 760 mAh/g;
preferably, the first charging and discharging efficiency of the lithium ion battery is more than 86%;
preferably, the lithium ion battery is charged and discharged for 50 times at 0.02C/0.2C, and the capacity retention rate of the lithium ion battery is more than 88%.
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