CN114551851A - Preparation method and application of silicon-carbon negative electrode material - Google Patents
Preparation method and application of silicon-carbon negative electrode material Download PDFInfo
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000004115 Sodium Silicate Substances 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 16
- 239000010703 silicon Substances 0.000 abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 125000004429 atom Chemical group 0.000 abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 239000010406 cathode material Substances 0.000 description 11
- 239000010405 anode material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
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
- H01M4/38—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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method and application of a silicon-carbon negative electrode material. After metal ions are removed from the silicate, the generated silicon dioxide has more atom vacancies, the problem of reduction of the cycle performance caused by volume expansion can be effectively solved, and when the silicate is sintered with graphene, oxygen atoms are abstracted from the silicon dioxide to form simple substance silicon with higher specific capacity, so that the specific capacity and the cycle performance of the material are improved.
Description
Technical Field
The invention belongs to the technical field of lithium battery cathode materials, and particularly relates to a preparation method and application of a silicon-carbon cathode material.
Background
Lithium ion batteries have the advantages of high specific capacity, high charging and discharging efficiency, good cycle performance and low cost, and thus become a hotspot of research work gradually. The rapid development of electronic products and new energy automobile technology puts higher requirements on lithium ion batteries. The cathode material is used as an important component of the lithium ion battery, which affects the specific energy and cycle life requirements of the battery, and is always the focus of lithium ion battery research. With the development of lithium ion battery technology, the development requirements of high capacity and small volume become more and more obvious, and therefore, the development of novel high capacity anode materials is urgent.
In the research and application of the lithium ion battery cathode material, the silicon-based cathode material has higher lithium storage capacity and lower voltage platform, and is one of the hot spots in the research of the lithium ion battery cathode material. The silicon-based material has the highest theoretical specific capacity, and the alloy formed by the silicon-based material is LixThe range of Si and x is 0-4.4, the theoretical specific capacity of pure silicon is 4200mAh/g, while the theoretical capacity of the current commercial negative electrode material natural graphite is only 372mAh/g, and the silicon has no solvation effect, so that the raw material is rich in storage, has higher stability than other metal materials, and is considered as the most expected negative electrode material of the high-capacity lithium ion battery.
However, the silicon negative electrode undergoes severe volume expansion and shrinkage during the lithium intercalation and deintercalation cycle, which causes the damage and pulverization of the material structure, and leads to pole piece powder removal, so that the electrode active material and the current collector lose electric contact, and the cycle performance of the battery is seriously affected. On the other hand, silicon itself is a semiconductor material and the conductivity is very low, and these problems prevent the silicon-based negative electrode material from being applied to a large scale in lithium ion batteries.
In order to solve the problem that the silicon negative electrode material is easy to generate stress cracking in the charging and discharging process to cause volume expansion to cause cycle performance deterioration, the following improvement methods are mainly adopted at present: reducing the particle size of active silicon particles, and preparing a nano-grade material to reduce the internal stress of volume change; the volume expansion of silicon is relieved by using the composite of the nano silicon material and other materials, such as silicon-carbon composite material, so that the cycle life of the silicon is prolonged. The related technology provides a material compounded by carbon nano-fiber and silicon material, and when the material is used as a lithium ion battery cathode material, the capacity and the cycle performance are improved. The researchers also adopt a hot gas deposition method to coat a layer of carbon material on the surface of the silicon simple substance, the specific capacity is more than 600mAh/g, the cycle performance is equivalent to that of the carbon material, and compared with the cycle performance of the simple substance silicon, the cycle performance is obviously improved. However, when the silicon-based negative electrode is used as a negative electrode of a lithium ion battery, the capacity and cycle performance of the silicon-based negative electrode need to be improved compared with the theoretical capacity of the silicon material.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method and application of a silicon-carbon negative electrode material.
According to one aspect of the invention, a preparation method of a silicon-carbon anode material is provided, which comprises the following steps:
s1: adding a metal salt solution into a sodium silicate solution for reaction, aging after the reaction is finished, and performing solid-liquid separation to obtain a silicate precipitate;
s2: calcining the silicate precipitate to obtain a calcined material;
s3: placing the calcined material in concentrated acid for hot soaking, and then carrying out solid-liquid separation and washing to obtain a wet material;
s4: and adding the wet material into the graphene dispersion liquid, evaporating to dryness, and heating the obtained dry material in an inert atmosphere to obtain the silicon-carbon negative electrode material.
In some embodiments of the invention, in step S1, the metal salt solution is at least one of a solution of a soluble magnesium, aluminum, nickel or manganese salt.
In some embodiments of the present invention, the metal salt solution is added to the sodium silicate solution at a rate of 5-20mL/min in step S1.
In some embodiments of the present invention, in step S1, the concentration of the metal salt solution is 0.5 to 2.5 mol/L.
In some embodiments of the present invention, in step S1, SiO is used2The concentration of the sodium silicate solution is 0.1-1.0 mol/L.
In some embodiments of the present invention, the sodium silicate is used in an amount of 1.05 to 1.1 times the theoretical amount in step S1.
In some embodiments of the invention, the temperature of the reaction in step S1 is 70-95 ℃.
In some embodiments of the present invention, in step S1, the aging time is 1-2 h.
In some embodiments of the present invention, the temperature of the calcination in step S2 is 700-1200 ℃. Further, the calcining time is 1-2 h.
In some embodiments of the invention, in step S3, the concentration of the concentrated acid is 4 to 12 mol/L; the temperature of the hot dipping is 60-120 ℃. Further, the time of the heat soaking is 10-120 min.
In some embodiments of the invention, in step S3, the liquid-to-solid ratio of the concentrated acid to the calcined material is 1 to 3 mL/g.
In some embodiments of the invention, in step S3, the concentrated acid is at least one of sulfuric acid, hydrochloric acid, or nitric acid.
In some embodiments of the invention, in step S4, the graphene dispersion is prepared by ultrasonically dispersing graphene in an organic solvent, and the mass ratio of silicon dioxide to graphene in the wet material is (0.05-0.2): 1.
in some preferred embodiments of the present invention, in step S4, the organic solvent is at least one of methanol, ethanol, acetone, tetrahydrofuran, NMP, DMF, dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate.
In some preferred embodiments of the present invention, in step S4, the concentration of the graphene dispersion is 0.5 to 3.0 g/L.
In some embodiments of the present invention, in step S4, the heating process is: firstly heating to 350-.
The invention also provides application of the preparation method in preparation of the lithium ion battery.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. according to the invention, firstly, metal salt reacts with sodium silicate to generate silicate precipitate, the precipitate is calcined at high temperature to crystallize silicate, then metal ions are removed by hot soaking with concentrated acid to prepare silicon dioxide with more atom vacancies, the silicon dioxide is mixed with graphene, under the condition of isolating oxygen, the graphene abstracts oxygen atoms from the silicon dioxide to further form oxygen-containing functional groups, and the silicon dioxide is reduced into a silicon simple substance, so that the silicon-carbon composite cathode material is obtained.
2. Because the silicate has more atom vacancies after metal ions are removed, the generated silicon dioxide can effectively relieve the problem of reduction of the cycle performance caused by volume expansion when used as a cathode material, and oxygen atoms are abstracted from the silicon dioxide when the silicon dioxide is sintered with graphene to form simple substance silicon with higher specific capacity, thereby improving the specific capacity and the cycle performance of the material.
Drawings
The invention is further described with reference to the following figures and examples, in which:
fig. 1 is an SEM image of a silicon carbon negative electrode material prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares a silicon-carbon anode material, and the specific process is as follows:
step 1, preparing a magnesium chloride solution A with the metal ion concentration of 1.0 mol/L;
step 2, preparing concentration (by SiO)2Calculated) 1.0mol/L sodium silicate solution B;
step 3, adding the magnesium chloride solution A prepared in the step 1 into the sodium silicate solution B prepared in the step 2 at the speed of 10mL/min for reaction, controlling the reaction temperature to be 70 ℃, and controlling the using amount of sodium silicate to be 1.05 times of the theoretical amount;
step 4, after the reaction is finished, continuing aging for 2 hours;
step 5, performing solid-liquid separation on the material to obtain a solid material;
step 6, calcining the solid material at the temperature of 1200 ℃ for 2h to obtain a calcined material;
step 7, placing the calcined material into sulfuric acid with the concentration of 12mol/L for soaking for 60min according to the liquid-solid ratio of 1mL/g, wherein the soaking temperature is 120 ℃;
step 8, performing solid-liquid separation on the materials, and washing the materials by pure water to obtain wet materials;
step 9, weighing graphene according to the mass ratio of 5% of silicon dioxide to graphene in the wet material, and ultrasonically dispersing the graphene in ethanol to obtain graphene dispersion liquid with the graphene concentration of 3.0 g/L;
step 10, adding the wet material into the graphene dispersion liquid, uniformly stirring, and evaporating to dryness to obtain a powder material;
and step 11, heating the powder material to 450 ℃ under inert gas, preserving heat for 2h, heating to 800 ℃ and preserving heat for 5h to obtain the silicon-carbon cathode material.
Example 2
The embodiment prepares a silicon-carbon anode material, and the specific process is as follows:
step 1, preparing an aluminum sulfate solution A with metal ion concentration of 2.0 mol/L;
step 2, preparing concentration (by SiO)2Calculated) 0.5mol/L sodium silicate solution B;
step 3, adding the aluminum sulfate solution A prepared in the step 1 into the sodium silicate solution B prepared in the step 2 at the speed of 20mL/min for reaction, controlling the reaction temperature to be 85 ℃, and enabling the use amount of sodium silicate to be 1.05 times of the theoretical amount;
step 4, after the reaction is finished, continuing aging for 1 h;
step 5, performing solid-liquid separation on the material to obtain a solid material;
step 6, calcining the solid material at the temperature of 1100 ℃ for 2 hours to obtain a calcined material;
step 7, soaking the calcined material in hydrochloric acid with the concentration of 8mol/L for 120min according to the liquid-solid ratio of 2mL/g, wherein the soaking temperature is 60 ℃;
step 8, performing solid-liquid separation on the materials, and washing the materials by pure water to obtain wet materials;
step 9, weighing graphene according to the mass ratio of the silicon dioxide to the graphene in the wet material of 10%, and ultrasonically dispersing the graphene in acetone to obtain graphene dispersion liquid with the graphene concentration of 0.5 g/L;
step 10, adding the wet material into the graphene dispersion liquid, uniformly stirring, and evaporating to dryness to obtain a powder material;
and step 11, heating the powder material to 350 ℃ under inert gas, preserving heat for 2h, heating to 1000 ℃, and preserving heat for 8h to obtain the silicon-carbon anode material.
Example 3
The embodiment prepares a silicon-carbon anode material, and the specific process is as follows:
step 1, preparing a nickel sulfate solution A with metal ion concentration of 2.5 mol/L;
step 2, preparing concentration (by SiO)2Calculated) 0.1mol/L sodium silicate solution B;
step 3, adding the metal salt solution A prepared in the step 1 into the sodium silicate solution B prepared in the step 2 at a speed of 5mL/min for reaction, controlling the reaction temperature to be 95 ℃, and using amount of the sodium silicate to be 1.1 times of theoretical amount;
step 4, after the reaction is finished, continuing aging for 2 hours;
step 5, performing solid-liquid separation on the material to obtain a solid material;
step 6, calcining the solid material at the temperature of 700 ℃ for 2 hours to obtain a calcined material;
step 7, soaking the calcined material in nitric acid with the concentration of 4mol/L for 120min according to the liquid-solid ratio of 3mL/g, wherein the soaking temperature is 70 ℃;
step 8, performing solid-liquid separation on the materials, and washing the materials by pure water to obtain wet materials;
step 9, weighing graphene according to the mass ratio of 20% of silicon dioxide to graphene in the wet material, and ultrasonically dispersing the graphene in tetrahydrofuran to obtain graphene dispersion liquid with the graphene concentration of 1.0 g/L;
step 10, adding the wet material into the graphene dispersion liquid, uniformly stirring, and evaporating to dryness to obtain a powder material;
and step 11, heating the powder material to 400 ℃ under inert gas, preserving heat for 2h, heating to 1200 ℃, and preserving heat for 12h to obtain the silicon-carbon anode material.
Comparative example 1
This comparative example prepared a silicon carbon negative electrode material, which was different from example 1 in that the wet material was replaced with commercially available nanoscale silica powder (analytical grade, 5-20nm), and the specific procedures were as follows:
step 1, weighing graphene according to the mass ratio of 5% of silicon dioxide powder to graphene, and ultrasonically dispersing the graphene in ethanol to obtain graphene dispersion liquid with the graphene concentration of 3.0 g/L;
step 2, adding silicon dioxide powder into the graphene dispersion liquid, uniformly stirring, and evaporating to dryness to obtain a powder material;
and 3, heating the powder material to 450 ℃ under inert gas, preserving heat for 2h, heating to 800 ℃ and preserving heat for 5h to obtain the silicon-carbon cathode material.
Comparative example 2
This comparative example prepared a silicon carbon negative electrode material, which was different from example 2 in that the wet material was replaced with commercially available silica powder (analytical grade), and the specific procedure was as follows:
step 1, weighing graphene according to the mass ratio of silicon dioxide powder to graphene being 10%, and ultrasonically dispersing the graphene in acetone to obtain graphene dispersion liquid with the graphene concentration being 0.5 g/L;
step 2, adding silicon dioxide powder into the graphene dispersion liquid, uniformly stirring, and evaporating to dryness to obtain a powder material;
and 3, heating the powder material to 350 ℃ under inert gas, preserving heat for 2h, heating to 1000 ℃, and preserving heat for 8h to obtain the silicon-carbon anode material.
Comparative example 3
This comparative example prepared a silicon carbon negative electrode material, which was different from example 3 in that the wet material was replaced with commercially available silica powder (analytical grade), and the specific procedure was as follows:
step 1, weighing graphene according to the mass ratio of 20% of silicon dioxide powder to graphene, and ultrasonically dispersing the graphene in tetrahydrofuran to obtain graphene dispersion liquid with the graphene concentration of 1.0 g/L;
step 2, adding silicon dioxide powder into the graphene dispersion liquid, uniformly stirring, and evaporating to dryness to obtain a powder material;
and 3, heating the powder material to 400 ℃ under inert gas, preserving heat for 2h, heating to 1200 ℃, and preserving heat for 12h to obtain the silicon-carbon anode material.
Test examples
And (3) uniformly stirring the silicon-carbon negative electrode materials obtained in the examples 1-3 and the comparative examples 1-3 with a conductive agent (SP) and a binder (CMC/SBR) to prepare electrode slurry, uniformly coating the slurry on a copper foil current collector with the thickness of 9 microns, drying for 12 hours at 105 ℃ under a vacuum condition, and cutting to obtain the negative electrode sheet. A 2032 type button cell is formed in a glove box filled with high-purity argon gas. The button cell is tested for charge and discharge performance, the charge and discharge cut-off voltage range is 5mV-1.5V, and the test temperature is 25 ℃. The test results are shown in table 1.
TABLE 1
As can be seen from table 1, the specific capacity and the cycle performance of the comparative example are lower than those of the examples, because the silicate precipitates of the examples have more atomic vacancies after removing metal ions by concentrated acid hot soaking, and when the silica is used as a negative electrode material, the problem of cycle performance reduction caused by volume expansion can be effectively alleviated, and meanwhile, more atomic vacancies can accommodate more lithium, so that the specific capacity is improved.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The preparation method of the silicon-carbon negative electrode material is characterized by comprising the following steps of:
s1: adding a metal salt solution into a sodium silicate solution for reaction, aging after the reaction is finished, and performing solid-liquid separation to obtain a silicate precipitate;
s2: calcining the silicate precipitate to obtain a calcined material;
s3: placing the calcined material in concentrated acid for hot soaking, and then carrying out solid-liquid separation and washing to obtain a wet material;
s4: and adding the wet material into the graphene dispersion liquid, evaporating to dryness, and heating the obtained dry material in an inert atmosphere to obtain the silicon-carbon negative electrode material.
2. The method according to claim 1, wherein in step S1, the metal salt solution is at least one of a soluble magnesium salt solution, an aluminum salt solution, a nickel salt solution, or a manganese salt solution.
3. The method according to claim 1, wherein in step S1, the concentration of the metal salt solution is 0.5-2.5 mol/L.
4. The method according to claim 1, wherein in step S1, SiO is used2The concentration of the sodium silicate solution is 0.1-1.0 mol/L.
5. The method according to claim 1, wherein the reaction temperature in step S1 is 70-95 ℃.
6. The method as claimed in claim 1, wherein the temperature of the calcination in step S2 is 700-1200 ℃.
7. The method according to claim 1, wherein in step S3, the concentration of the concentrated acid is 4 to 12 mol/L; the temperature of the hot dipping is 60-120 ℃.
8. The preparation method according to claim 1, wherein in step S4, the graphene dispersion liquid is prepared by ultrasonically dispersing graphene in an organic solvent, and the mass ratio of silicon dioxide to graphene in the wet material is (0.05-0.2): 1.
9. the method of claim 1, wherein in step S4, the heating process is: firstly heating to 350-.
10. Use of the preparation process according to any one of claims 1 to 9 for the preparation of lithium ion batteries.
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