CN114551841A - Composite material and preparation method thereof, negative plate and secondary battery - Google Patents
Composite material and preparation method thereof, negative plate and secondary battery Download PDFInfo
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- CN114551841A CN114551841A CN202210184630.3A CN202210184630A CN114551841A CN 114551841 A CN114551841 A CN 114551841A CN 202210184630 A CN202210184630 A CN 202210184630A CN 114551841 A CN114551841 A CN 114551841A
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- mxene
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000005416 organic matter Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000005530 etching Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 8
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 8
- 229940079864 sodium stannate Drugs 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010013 Ti2SnC Inorganic materials 0.000 description 1
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HTHDWDSBYOUAFF-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin;trihydrate Chemical compound O.O.O.[K+].[K+].[O-][Sn]([O-])=O HTHDWDSBYOUAFF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
- C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
- C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
- C04B35/5618—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides based on titanium aluminium carbides
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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- 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
- H01M4/387—Tin or alloys based on tin
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- 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
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- 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
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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
- 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
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Abstract
The invention belongs to the technical field of secondary batteries, and particularly relates to a composite material and a preparation method thereof, a negative plate and a secondary battery, wherein the preparation method comprises the following steps: s1, adding the tin salt and the alkaline organic matter into the first solvent, stirring and mixing to obtain a first mixed solution; s2, heating and pressurizing the first mixed solution, centrifuging, washing and removing impurities to obtain powder; s3, heating and reducing the powder to obtain nano tin powder; s4, performing acid etching and water washing on the MAX phase ceramic material to obtain an MXene material; and S5, adding the nano tin powder and the MXene material into a second solvent for ultrasonic treatment, and cooling to obtain the composite material. According to the preparation method disclosed by the invention, the elementary tin substance is combined with the MXene material, the advantages of the elementary tin substance and the MXene material are combined, and meanwhile, the MXene material provides an expansion buffer layer structure for the elementary tin substance, so that the cycle performance is improved, the prepared composite material has excellent rate performance, and quick charging can be realized.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a composite material and a preparation method thereof, a negative plate and a secondary battery.
Background
As a novel green energy source, the lithium ion battery is more and more widely applied to daily life of people and has higher and higher requirements. However, the negative electrode material is an important component thereof. At present, the main current material of the negative electrode is a graphite material, but the theoretical specific capacity (342mAh & g) is lower-1) Will not meet the needs of people in the future, and in addition, the lower lithium intercalation potential thereof causes safety problems. Therefore, it is necessary to find a negative electrode material to replace graphite.
The metallic tin not only has higher specific capacity (990 mAh.g)-1) The conductive tin has good conductivity and moderate lithium intercalation potential, can improve the safety performance of the lithium battery in the circulating process, and is one candidate for replacing graphite, but the tin has poorer circulating performance due to pulverization and inactivation caused by larger volume expansion in the circulating process, and is difficult to reach the use standard.
Mxene is a novel two-dimensional metal carbide/nitride that has attracted a great deal of attention and research to many experts and scholars. The Mxene has unique interlayer spacing, good mechanical property, high conductivity and good hydrophilicity. There are some drawbacks. For example, it has a low theoretical specific capacity, is prone to interlayer stacking, and is difficult to be applied to electrode materials, so that it is necessary to research a new negative electrode material.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the preparation method of the composite material is provided, and the elementary tin is combined with the MXene material to obtain the negative electrode material which has good performance and can be rapidly charged and discharged.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a composite material comprises the following preparation methods:
step S1, adding tin salt and alkaline organic matter into a first solvent, stirring and mixing to obtain a first mixed solution;
step S2, heating and pressurizing the first mixed solution, centrifuging, washing and removing impurities to obtain powder;
step S3, heating and reducing the powder under reducing gas to obtain nano tin powder;
s4, selecting a MAX-phase ceramic material, and performing acid etching and water washing on the MAX-phase ceramic material to obtain an MXene material;
and step S5, adding the nano tin powder and the MXene material into a second solvent for ultrasonic treatment, and cooling to obtain the composite material.
According to the invention, a hydrothermal method and a high-temperature reduction method are used for preparing the nano-sized tin simple substance, so that the large-volume expansion of the tin simple substance in the circulation process is reduced, the pulverization and the inactivation of the material are reduced, and the circulation performance is improved; and the simple substance tin is compounded with MXene with a layered structure, and the simple substance tin is arranged in the layered structure of the MXene material by combining the characteristics that the simple substance tin has good conductivity and suitable lithium intercalation potential and the characteristics that the MXene material has good mechanical property, higher conductivity and hydrophilicity, so that the simple substance tin is buffered for the volume expansion of the simple substance tin, the cycle performance of the material is prolonged, meanwhile, the layered structure reduces the direct contact of electrolyte to the simple substance tin, the service life of the material is prolonged, the material has excellent rate performance, and the rapid charge and discharge can be realized. Meanwhile, the prepared material is cooled, so that the layered structure can be retained to a great extent, and the material performance is better. Wherein the first solvent is deionized water and absolute ethyl alcoholAnd mixing the mixed solution in a volume ratio of 1:6, wherein the second solvent is a mixed solution of deionized water and absolute ethyl alcohol in a volume ratio of 2:5, the centrifugal rotating speed in the step S2 is 500-3500 rpm/min, deionized water and alcohol are used for washing, Ar or hydrogen is used as a reducing gas, and liquid nitrogen is used for freezing in a freeze dryer. The MAX phase ceramic material may be Ti3AlC2Or Ti2SnC。
Wherein the weight part ratio of the tin salt to the alkaline organic matter in the step S1 is 1-1.5: 2-3. The tin salt and the alkaline organic matter are added according to a certain weight part ratio, so that the tin salt reacts more fully, and the obtained simple substance of tin is purer. The weight ratio of the tin salt to the alkaline organic matter can be 1:2, 1:2.5, 1:2.8, 1:3, 1.3:2, 1.3: 3. 1.5:2, 1.3:2.5, 1.3:2.6, 1:2.4, 1:2.9, 1.7: 2.
In the step S1, the tin salt is sodium stannate, potassium stannate, a combination of the sodium stannate and the potassium stannate, a hydrate of the sodium stannate and a hydrate of the potassium stannate, and the alkaline organic substance is one or a mixture of several of methylamine, aniline and urea. Sodium stannate, potassium stannate and a combination of the sodium stannate and the potassium stannate are used as the stannate, and sodium stannate hydrate and potassium stannate hydrate can avoid introducing impurities, so that a simple substance of tin obtained by reaction is purer.
Wherein the heating and pressurizing temperature in the step S2 is 140-160 ℃, and the pressure is 100-500 Mpa. The heating temperature can be 140 deg.C, 142 deg.C, 146 deg.C, 148 deg.C, 150 deg.C, 153 deg.C, 154 deg.C, 158 deg.C, and 160 deg.C; the pressure is 100MPa, 120MPa, 150MPa, 180MPa, 220MPa, 260MPa, 320MPa, 360MPa, 380MPa, 400MPa, 460MPa, or 500 MPa.
Wherein the heating temperature in the step S3 is 800-1000 ℃, and the heating time is 1-5 h. The heating temperature is 800 deg.C, 850 deg.C, 890 deg.C, 900 deg.C, 920 deg.C, 950 deg.C, 980 deg.C, 1000 deg.C; the heating time is 1h, 1.2h, 1.5h, 1.9h, 2.5h, 2.9h, 3h, 3.4h, 3.8h, 4h, 4.5h and 5 h.
Wherein the MXene material in the step S4 is Ti3C2、Ti2C, one or a mixture of two of the C.
Wherein, the weight ratio of the nano tin powder to the MXene material in the step S5 is 5-25: 1-2. The weight portion ratio of the nano tin powder to the MXene material can be 5:1, 5:1.5, 5:1.8, 5:2, 8:1, 9:1, 10:1, 12:1, 13:1, 15:1, 18:1, 21:1, 23:1, 25:1, 13:2, 15:2, 18.5:1, 21:2, 23:2, 25:2, 23:4, 23:3, 25:1, 25:3, 25:4 and 24: 5.
The second purpose of the invention is: aiming at the defects of the prior art, the composite material is provided, has good rate capability and can realize rapid charge and discharge.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite material is prepared by the preparation method of the composite material.
The third purpose of the invention is that: aiming at the defects of the prior art, the negative plate has good rate capability and can realize rapid charge and discharge.
In order to achieve the purpose, the invention adopts the following technical scheme:
a negative plate comprises a negative current collector and an active material arranged on at least one surface of the negative current collector, wherein the active material is the composite material.
The fourth purpose of the invention is that: in view of the deficiencies of the prior art, a secondary battery is provided, which has excellent rate capability and can realize rapid charging and discharging.
In order to achieve the purpose, the invention adopts the following technical scheme:
a secondary battery comprises the negative plate.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, a hydrothermal method and a high-temperature reduction method are used for preparing the nano-sized tin simple substance, so that the large-volume expansion of the tin simple substance in the circulation process is reduced, the pulverization and the inactivation of the material are reduced, and the circulation performance is improved; and the simple substance tin is compounded with MXene with a layered structure, and the simple substance tin is arranged in the layered structure of the MXene material by combining the characteristics that the simple substance tin has good conductivity and suitable lithium intercalation potential and the characteristics that the MXene material has good mechanical property, higher conductivity and hydrophilicity, so that the simple substance tin is buffered for the volume expansion of the simple substance tin, the cycle performance of the material is prolonged, meanwhile, the layered structure reduces the direct contact of electrolyte to the simple substance tin, the service life of the material is prolonged, the material has excellent rate performance, and the rapid charge and discharge can be realized. Meanwhile, the prepared material is cooled, so that the layered structure can be retained to a great extent, the direct contact of the simple substance tin and the electrolyte is reduced, meanwhile, a buffer body is provided for the simple substance tin, the cycle performance is improved, the prepared composite material has excellent rate performance, and the rapid charging can be realized.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
1. 1.3g of potassium stannate trihydrate powder (K) of a tin salt2SnO3·3H2O) and 3g of basic organic urea (CH)4N2O) adding the medicine into a first solvent, wherein the first solvent is a mixed solution formed by mixing deionized water and absolute ethyl alcohol according to the volume ratio of 1:6, and stirring the solution for 2 hours by using a magnetic stirrer to uniformly mix the solution to obtain a first mixed solution.
2. The first mixture was placed in an autoclave at 140 ℃ for 5 hours under a pressure of 200 MPa. The excess impurities were then washed off in a centrifuge with deionized water and alcohol to give a white powder. Finally, in Ar/H2Heating to 900 ℃ in a reducing atmosphere, and keeping for 3 hours to obtain elemental tin powder.
3. Using the Mxene material obtained by acid etching and water washing of MAX phase ceramic material;
4. adding the elemental tin powder and the Mxene material into a second solvent according to the weight part ratio of 23:2, wherein the second solvent is a mixed solution of deionized water and absolute ethyl alcohol in a volume ratio of 2:5, and then carrying out ultrasonic treatment for 6H; the above-mentioned sonicated mixed solution was placed in liquid nitrogen to be rapidly frozen, and then a bulk powder of Sn @ Mxene, i.e., a composite material, was prepared in a freeze-dryer.
Example 2
The difference from example 1 is that: the weight portion ratio of the tin salt to the alkaline organic matter is 1.5: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is that: the weight portion ratio of the tin salt to the alkaline organic matter is 1.5: 2.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is that: the weight portion ratio of the tin salt to the alkaline organic matter is 1.5: 3.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is that: the weight portion ratio of the tin salt to the alkaline organic matter is 1:2.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is that: the weight portion ratio of the tin salt to the alkaline organic matter is 1: 3.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that: the weight portion ratio of the nano tin powder to the MXene material is 23: 5.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that: the weight portion ratio of the nano tin powder to the MXene material is 23: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that: the weight portion ratio of the nano tin powder to the MXene material is 15: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is that: the weight portion ratio of the nano tin powder to the MXene material is 5: 2.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is that: the heating temperature in step S3 was 900 ℃ and the heating time was 5 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 12
The difference from example 1 is that: the heating temperature in step S3 was 950 ℃ and the heating time was 3 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 13
The difference from example 1 is that: the heating temperature in step S3 was 800 ℃ and the heating time was 3 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Example 14
The difference from example 1 is that: the heating temperature in step S3 was 900 ℃ and the heating time was 2 hours.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from example 1 is that: and step S5, adding the nano tin powder and the MXene material into a second solvent for ultrasonic treatment to obtain the composite material.
The rest is the same as embodiment 1, and the description is omitted here.
And (3) performance testing: the composite materials prepared in example 1 and comparative example 1 were applied to a battery to perform a rate capability test in an oven at 25 ℃ and a cycle performance test at a current density of 0.2A/g, and the test results are reported in tables 1 and 2.
TABLE 1
TABLE 2
From the above table 1 and table 2, we can see that in the rate performance test, we set the gradient current with the current density of 0.2, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0 and 0.2A/g, and we can see that the Sn @ Mxene composite electrode material has better rate performance. Secondly, the Sn @ Mxene electrode material has higher specific capacity and more stable capacity retention rate in a cycle test of small current of 0.2A/g. Indicating that the volume expansion of the tin-based material is greatly improved.
The composite materials prepared in examples 1 to 14 and comparative example 1 were applied to a battery and tested for rate capability and cycle performance in an oven at 25 ℃, and the test results are reported in table 3.
Rate capability: the button full cell to be tested is stood for 30 minutes in an environment of 25 plus or minus 3 ℃, is charged with constant current at the rate of 0.1C until the voltage is 4.4V (rated voltage), is charged with constant voltage until the current is 0.025C, is discharged to 3V (cut-off voltage) at the rates of 0.1C, 0.2C, 0.5C, 1C and 2C respectively, and is recorded with the gram discharge capacity under different discharge rates.
Cycle performance: charging the lithium ion secondary battery to 4.25V at a constant current of 1C at 25 ℃, then charging to 0.05C at a constant voltage of 4.25V, standing for 5min, and then discharging to 2.8V at a constant current of 1C, wherein the process is a charge-discharge cycle process, and the discharge capacity at this time is the discharge capacity of the first cycle. The lithium ion secondary battery was subjected to 400-cycle charge/discharge tests in accordance with the above-described method, and the discharge capacity per one cycle was recorded. The cycle capacity retention (%) was 400 cycles of discharge capacity/first cycle of discharge capacity × 100%.
TABLE 3
As can be seen from table 1, the composite material obtained by the preparation method of the present invention has better capacity retention rate and higher rate performance compared to the prior art. From the comparison of examples 1 to 6, it is found that when the weight ratio of the tin salt to the basic organic substance is set to 1.3:3, the composite material prepared has better performance. According to the comparison of the examples 1 and 7-10, when the weight part ratio of the nano tin powder to the MXene material is 23:2, the prepared composite material has better performance. As shown by comparing examples 1 and 11 to 14, when the heating temperature in step S3 is set to 900 ℃ and the heating time is set to 3 hours, the prepared composite material has better performance.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious modifications, substitutions or alterations based on the present invention will fall within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The preparation method of the composite material is characterized by comprising the following preparation methods:
step S1, adding tin salt and alkaline organic matter into a first solvent, stirring and mixing to obtain a first mixed solution;
step S2, heating and pressurizing the first mixed solution, centrifuging, washing and removing impurities to obtain powder;
step S3, heating and reducing the powder under reducing gas to obtain nano tin powder;
s4, selecting a MAX-phase ceramic material, and performing acid etching and water washing on the MAX-phase ceramic material to obtain an MXene material;
and step S5, adding the nano tin powder and the MXene material into a second solvent for ultrasonic treatment, and cooling to obtain the composite material.
2. The method for preparing the composite material according to claim 1, wherein the weight ratio of the tin salt to the basic organic substance in the step S1 is 1-1.5: 2-3.
3. The method for preparing the composite material according to claim 1, wherein the stannic salt in the step S1 is sodium stannate, potassium stannate or a combination of the two, a hydrate of sodium stannate and a hydrate of potassium stannate, and the basic organic substance is one or a mixture of several of methylamine, aniline and urea.
4. The method for preparing a composite material according to claim 1, wherein the heating and pressurizing temperature in the step S2 is 140 ℃ to 160 ℃, and the pressure is 100MPa to 500 MPa.
5. The method for preparing the composite material according to claim 1, wherein the heating temperature in the step S3 is 800-1000 ℃, and the heating time is 1-5 h.
6. The method for preparing the composite material according to claim 1, wherein the MXene material in the step S4 is Ti3C2、Ti2C, one or a mixture of two of the C.
7. The method for preparing the composite material according to claim 1, wherein the weight part ratio of the nano tin powder to the MXene material in the step S5 is 5-25: 1-5.
8. A composite material produced by the method for producing a composite material according to any one of claims 1 to 7.
9. A negative electrode sheet comprising a negative electrode current collector and an active material disposed on at least one surface of the negative electrode current collector, wherein the active material is the composite material according to claim 8.
10. A secondary battery comprising the negative electrode sheet according to claim 9.
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