CN114551833B - Coral-morphology tin dioxide@carbon composite nanomaterial and preparation method thereof, semi-solid negative electrode slurry and semi-solid lithium ion battery - Google Patents
Coral-morphology tin dioxide@carbon composite nanomaterial and preparation method thereof, semi-solid negative electrode slurry and semi-solid lithium ion battery Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000007787 solid Substances 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 20
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011149 active material Substances 0.000 claims abstract description 13
- 235000014653 Carica parviflora Nutrition 0.000 claims abstract description 10
- 241000243321 Cnidaria Species 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 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 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical group O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000006256 anode slurry Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000002033 PVDF binder Substances 0.000 abstract description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 238000012827 research and development Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 238000007599 discharging Methods 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
Abstract
The invention provides a coral morphology tin dioxide@carbon composite nanomaterial and a preparation method thereof, semi-solid negative electrode slurry and a semi-solid lithium ion battery. Meanwhile, polyvinylidene fluoride is added as an additive when the semisolid lithium ion battery slurry is prepared, so that the formed semisolid slurry electrode has higher stability. Compared with the traditional preparation process of the lithium ion battery electrode, the preparation process of the semi-solid slurry electrode does not need complex preparation processes such as coating, drying and the like, is favorable for large-scale production and research and development of novel electrode materials, has the characteristic of no current collector, and can avoid capacity attenuation caused by the fact that active materials form cracks to fall off from the current collector in the circulation process, so that the service life of the battery is greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a tin dioxide@carbon composite nanomaterial with coral morphology, a preparation method of the tin dioxide@carbon composite nanomaterial, battery negative electrode slurry and a semi-solid lithium ion battery.
Background
The current commercial lithium ion battery cathode is graphite, and the problems of low capacity, poor stability, more side reactions caused by low purity, poor multiplying power performance and the like make people urgently need to find a material which has stable structure and high capacity and can adapt to high-current density charge and discharge to replace natural graphite as a chargeable lithium ion battery cathode.
Among a plurality of materials, the tin dioxide can be used as a substitute material of the negative electrode of the next generation lithium ion battery due to the advantages of low production cost, simple preparation process, stable structure, suitability for high-current charge and discharge and the like. The current preparation technology of the anode material is mostly a coating method, the prepared material and conductive carbon black are ground and then dispersed in N-methyl pyrrolidone to form slurry, then the slurry is coated on a current collector copper foil with a certain thickness, and the current collector copper foil is dried and then subjected to hot rolling and slicing to obtain the anode electrode slice. The complicated electrode slice preparation process relates to raw material proportion, slurry concentration, coating thickness, drying time, fitting degree with a current collector, slicing process and the like, so that errors affecting the performance of the finally prepared electrode slice are increased, and the research and development and preparation cost of the electrode are greatly improved. In addition, in the process of circulation, the surface of the electrode plate is cracked due to volume expansion of the material in the process of charging and discharging, so that the electrode material is separated from a current collector, and the irreversible attenuation of the battery capacity is caused.
Disclosure of Invention
The invention aims to provide a coral-shaped tin dioxide@carbon composite nanomaterial and a preparation method thereof, wherein a loose carbon layer is arranged in the prepared composite material, so that the overall conductivity of the material is improved; and the preparation method is simple and the cost is low.
The invention also aims at providing the semi-solid negative electrode slurry, which is prepared by adopting the coral-shaped tin dioxide@carbon composite nanomaterial as an active material, has high capacity and low cost, and can replace the current commercial graphite negative electrode.
The invention provides a semi-solid lithium ion battery, which is prepared by adopting a coral-shaped tin dioxide@carbon composite nanomaterial as an active material and adopting semi-solid slurry without a current collector, so that the semi-solid lithium ion battery has the characteristics of higher capacity, capability of avoiding the electrode plate from cracking in the circulation process and falling off from the current collector, and high stability. The obtained semisolid lithium ion battery has the advantages of novel, high capacity, low cost and good stability.
The specific technical scheme of the invention is as follows:
the preparation method of the coral-shaped tin dioxide@carbon composite nanomaterial specifically comprises the following steps:
and dissolving tin salt and water, uniformly mixing to obtain a mixed solution, carrying out hydrothermal reaction, and centrifuging, washing and drying after the reaction is finished to obtain the coralloid tin dioxide@carbon composite material.
The molar ratio of carbon source to tin salt was 0.1:1-3.0:1, wherein the concentration of the tin salt in the mixed solution is 0.1mol L -1 -2.0mol L -1 Preferably 0.25mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the carbon source in water is 0.1-2.0mol L -1 Preferably 0.5mol L -1 ；
Further, the tin salt is tin tetrachloride pentahydrate (SnCl) 4 ·5H 2 O); the carbon source is glucose, fructose or sucrose.
The hydrothermal reaction condition is 90-190 deg.c and the reaction time is 0.5-20 hr.
The coral-shaped tin dioxide@carbon composite nanomaterial provided by the invention is prepared by the method, the length range of the material is 1.0-3.0 mu m, the coral-shaped pipe diameter is 300-400nm, the outer part is a tin dioxide shell, and amorphous carbon particles are wrapped inside the material.
In the preparation method of the coral-shaped tin dioxide@carbon nanocomposite provided by the invention, tin tetrachloride pentahydrate (SnCl) 4 ·5H 2 O) is used as tin salt, sucrose is used as carbon source, and the tin salt and the sucrose are reacted in deionized water by a one-step hydrothermal method, washed and driedAnd obtaining the compound of tin dioxide and carbon with coral morphology. Under heating, tin tetrachloride is hydrolyzed, wherein Sn 4+ Combined with hydroxyl radical in water to generate Sn (OH) 4 Which has an oxidizing property and dehydrates sucrose to form carbon particles, thereby being encapsulated in Sn (OH) 4 As the reaction proceeds, sn (OH) encapsulating the carbon 4 Mutually fused, gradually grown outwards into a curved structure, and finally coated with Sn (OH) along with mutual dehydration reaction between hydroxyl groups 4 Gradually converts to tin dioxide and tightly encapsulates the internal carbon. The prepared tin dioxide@carbon composite material is used as a negative electrode of a lithium ion battery, so that the conductivity of the tin dioxide can be improved, and the tin dioxide has excellent stability due to a three-dimensional structure. When applied to a semi-solid lithium ion battery, the material has the characteristics of simple and convenient process, high specific capacity and easy control.
The semi-solid negative electrode slurry provided by the invention is prepared by adopting the coral-shaped tin dioxide@carbon composite nanomaterial as an active material.
The preparation method for preparing the semi-solid negative electrode slurry comprises the following steps: grinding the coral-shaped tin dioxide@carbon composite nanomaterial and conductive carbon black, dispersing the ground powder in electrolyte under magnetic stirring, adding a high molecular polymer into the dispersed slurry, and continuously stirring to form homogeneous slurry;
the mass ratio of the coral-shaped tin dioxide@carbon composite nanomaterial to the conductive carbon black is 1:4-8:1, preferably 2:1, and the mass volume ratio of the coral-shaped tin dioxide@carbon composite nanomaterial to the electrolyte is 1:20-1:5 g mL -1 Preferably 1:10g mL -1 。
The electrolyte is binary electrolyte, and LiPF is used for preparing the electrolyte 6 Dissolved in a solution formed by mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in equal volumes, liPF 6 The concentration was 1.0M; the electrolyte serves as a dispersant for the solid powder.
The added high polymer is PVDF, and the ratio of the mass of the PVDF to the mass of the coral morphology tin dioxide@carbon composite nanomaterial is 1:10-1:2, preferably 1:4.
The stirring time is 2-24 h.
The semisolid lithium ion battery provided by the invention is prepared from the semisolid negative electrode slurry.
Compared with the traditional solid electrode, the semi-solid electrode has the advantages that the active material is dispersed in the electrolyte, so that the steps of slurry coating, drying, hot rolling and the like are omitted in the preparation process of the electrode, the preparation process and flow are greatly reduced, capacity attenuation caused by the falling of the electrode material from a current collector is avoided, and the semi-solid electrode can not generate cracks in the charging and discharging process compared with the traditional electrode, so that the cycle life is greatly prolonged. The active material in the semi-solid slurry electrode is in a suspension state under the stirring condition, and the material can be precipitated at the bottom due to the influence of gravity along with the stopping of stirring, so that the high-molecular polymer added in the invention can be dissolved and form a framework in the environment of electrolyte to form a conductive network, and the precipitation of the active material is prevented. When the volume of the active material expands in the charge and discharge process, the active material is dispersed in the electrolyte, so that compared with the traditional electrode, the active material does not generate cracks to lead the capacity to be attenuated, is beneficial to rapid electron ion transmission and can improve the performance of the battery.
The invention takes tin salt as a raw material and sucrose as a carbon source, and is synthesized by a one-step hydrothermal method to obtain the lithium ion battery cathode. Meanwhile, when the semisolid lithium ion battery slurry is prepared, PVDF is added as an additive, so that the formed semisolid slurry electrode has higher stability. Compared with the traditional preparation process of the lithium ion battery electrode, the preparation process of the semi-solid slurry electrode does not need complex preparation processes such as coating, drying and the like, is favorable for large-scale production and research and development of novel electrode materials, has the characteristic of no current collector, and can avoid capacity attenuation caused by the fact that active materials form cracks to fall off from the current collector in the circulation process, so that the service life of the battery is greatly prolonged.
Compared with the prior art, the invention has the following advantages:
(1) Because the carbon cores in the middle of the method are gradually fused along with the reaction, and the carbon cores are combined in a non-chemical bond mode, the prepared tin dioxide@carbon composite material is internally loose carbon, and the improvement of the overall conductivity of the material is facilitated;
(2) The prepared tin dioxide@carbon negative electrode material is applied to a lithium ion battery negative electrode, and has higher specific capacity and better capacity reversibility;
(3) The semi-solid slurry electrode can avoid the falling of active substances caused by the volume expansion of the material in the charge and discharge process, is beneficial to regulating and controlling the content of the active substances in the battery, and is beneficial to the research and development of the material and the reduction of the process cost of the battery;
(4) The raw materials are low in price, the preparation process is simple, and the large-scale production can be performed.
Drawings
FIG. 1 is an XRD pattern of coralloidal tin dioxide @ carbon prepared in example 1;
FIG. 2 is an SEM image of coralloidal tin dioxide @ carbon prepared in example 1;
FIG. 3 is a TEM image of coralloidal tin dioxide @ carbon prepared in example 1;
FIG. 4 is a TGA graph of coralloidal tin dioxide @ carbon prepared in example 1;
FIG. 5 is a diagram of a semi-solid slurry electrode prepared in example 3;
fig. 6 is a graph showing the cycle performance of the semi-solid slurry lithium ion battery of example 4;
fig. 7 is a charge-discharge curve diagram of the semi-solid slurry lithium ion battery in example 4;
fig. 8 is a graph of the rate performance of the semi-solid slurry lithium ion battery of example 4;
FIG. 9 is a graph showing the cycle performance of the electrode sheet lithium ion battery of comparative example 1;
fig. 10 is a charge-discharge graph of the electrode sheet lithium ion battery in comparative example 1.
Detailed Description
The present invention will be described in detail with reference to examples and drawings.
Example 1
The preparation method of the coral-shaped tin dioxide@carbon composite nanomaterial specifically comprises the following steps:
10mmol of SnCl was weighed 4 ·5H 2 O is added into a beaker, 40mL of deionized water is added, magnetic stirring is carried out to dissolve the deionized water, then 20mmol of sucrose is added, the mixed solution is transferred into a 50mL polytetrafluoroethylene reaction kettle liner after the dissolution is completed, and the reaction is carried out for 6 hours at 180 ℃; after the reaction is finished, respectively carrying out centrifugal washing by using water and absolute ethyl alcohol, wherein the rotating speed of a centrifugal machine is 6000 revolutions per minute, and then carrying out vacuum drying on the washed product at 60 ℃ for 12 hours to obtain a final product; the XRD pattern is shown in figure 1, and the prepared nano composite material is composed of tin dioxide, and the carbon coated inside is difficult to observe from the figure; the SEM diagram is shown in FIG. 2, and the prepared tin dioxide@carbon nanocomposite can be seen to have a curved and wrapped coral shape; FIG. 3 is a TEM image of a tin dioxide@carbon composite material, from which it can be seen that the prepared composite material is of solid structure and the diameter of the prepared coral tentacle is about 400 nm; from the thermogravimetric curve in fig. 4, it can be seen that the carbon content in the composite material is 56%.
Example 2
Preparation of a tin dioxide@carbon electrode plate based on coral morphology and application of the tin dioxide@carbon electrode plate as a lithium battery negative electrode material comprise the following steps:
(1) Preparation of slurry: uniformly mixing the prepared tin dioxide@carbon nanocomposite, conductive carbon black and CMC according to the ratio of 7:2:1 or 8:1:1, adding a proper amount of SBR by using water as a dispersing agent, and magnetically stirring for 8-12 hours to form uniform slurry.
(2) Coating the stirred slurry on clean copper foil with a certain thickness by a coating method, drying in a vacuum drying oven at 60-80 ℃ for 8-12 hours, and cutting into small wafer electrodes with a certain size by a cutting machine.
(3) The electrode sheet was assembled into a 2032-type coin cell in a glove box filled with high purity argon gas (water value and oxygen value: 0.01ppm or less). LiPF is put into 6 Dissolved in a solution formed by mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in equal volumes, liPF 6 At a concentration of 1.0M to obtain an electrolyte. The method for specifically assembling the battery comprises the following steps: and (3) dropwise adding one drop of electrolyte on the electrode shell, then placing an electrode plate (the small-disk electrode), dropwise adding two drops of electrolyte to wet the surface of the electrode, placing a Celgard diaphragm on the electrode plate, dropwise adding one drop of electrolyte on the diaphragm, then placing a lithium sheet as a counter electrode, then placing a gasket and an elastic sheet as supports, and tightly packaging the battery by using a hydraulic press.
Example 3
The preparation method of the semi-solid electrode slurry comprises the following specific steps: grinding and mixing 0.1g of the prepared coralloid tin dioxide@carbon nanocomposite with 0.05g of conductive carbon black, then magnetically stirring and dispersing a uniformly ground sample in 1mL of the electrolyte in a glove box, adding 0.025g of PVDF after uniformly stirring and dispersing, and continuously stirring for 2-24 hours to obtain the semi-solid slurry. It can be seen from fig. 5 that the semi-solid slurry has good fluidity and uniformity, and that it is not delaminated after 48 hours of standing, as can be seen from the right-most graph in fig. 5.
Preparation of a semisolid lithium ion battery: and directly dripping the prepared semi-solid electrode slurry on an electrode shell, and calculating the content of active materials in the battery according to the mass difference before and after the electrode shell is dripped with the slurry. Then a piece of glass fiber soaked by binary electrolyte is covered as a diaphragm, then a piece of lithium piece is placed as a counter electrode, then a gasket and an elastic piece are placed as a support, and after a battery cathode shell is placed, the battery is pressed on a hydraulic press.
Example 4
Electrochemical performance test of semi-solid lithium ion battery:
after the semi-solid lithium ion battery assembled in example 3 was left for 8 to 12 hours, the battery was assembled in a state of 0.1 to 0.1A g -1 As shown in FIG. 6 and FIG. 7, the battery capacity was stabilized at 528mAh g after 100 cycles -1 From left to right, as can be seen from fig. 7, there is one plateau at about 1.0V on the discharge curve, and the second plateau is at about 0.5V; for the charging process, there is a plateau around 0.7V and 1.3V respectively.
The rate performance of the battery was tested at the same time, and a current density gradient of 0.1A g was set -1 ～1.0A g -1 . The measured rate performance is shown in FIG. 8, from which it can be seen that the prepared semi-solid lithium ion battery was at 0.1A g -1 Exhibits a current density of 804mAh g -1 Even at 1.0A g -1 Can still show 165mAh g at a high current density -1 And again back to 0.1A g -1 The battery still can show 771mAh g after the current density of (2) -1 The stable capacity of (2) shows that the battery can well adapt to high-current charge and discharge, and the result is shown in figure 8.
Comparative example 1
Electrochemical performance test of electrode slice lithium ion battery:
after the assembled battery of example 2 was left for 8 to 12 hours, the battery was assembled at 0.1 to 0.1A g -1 The results of the battery cycle performance test and the charge and discharge performance test under the current density of (1) show that the battery also shows excellent electrochemical performance, and the solid electrode can not relieve the volume expansion of the material in the charge and discharge process, so that the material is separated from the electrode, and only 150.6mAh g is reserved after 100 times of cycles -1 Is a function of the capacity of the battery.
The semi-solid battery is not a traditional electrode slice battery, so that the volume expansion of the material in the charging and discharging process can not lead to the cracking of the electrode slice to fall off from the current collector, thereby causing irreversible reduction of capacity, and the comparison of fig. 7 and fig. 10 shows that the semi-solid electrode is the same as the charging and discharging curve of the traditional electrode, and the charging and discharging curve of the battery is not changed due to the fact that the semi-solid battery is manufactured, and the platform of the charging and discharging curve is not changed.
The foregoing detailed description of a novel battery and its preparation technology, which are provided by the above-mentioned embodiments with respect to a tin dioxide@carbon nanocomposite having a coral morphology and a preparation method thereof, a rechargeable lithium ion battery and a semi-solid lithium ion battery, is illustrative and not limiting, and several embodiments can be listed according to the limited scope, so that the invention shall fall within the scope of protection of the present invention without departing from the general inventive concept.
Claims (10)
1. The preparation method of the coral-shaped tin dioxide@carbon composite nanomaterial is characterized by specifically comprising the following steps of:
dissolving tin salt and a carbon source in water, uniformly mixing to obtain a mixed solution, carrying out hydrothermal reaction, and centrifuging, washing and drying after the reaction is finished to obtain a coralloid tin dioxide@carbon composite material;
the coralloid tin dioxide@carbon composite material is internally provided with a loose carbon layer, and is externally provided with a tin dioxide shell, and amorphous carbon particles are wrapped inside;
the coralloid tin dioxide@carbon composite material is used for a semi-solid lithium ion battery.
2. The method according to claim 1, wherein the molar ratio of the carbon source to the tin salt is 0.1:1-3.0:1.
3. The method according to claim 1 or 2, wherein the concentration of the tin salt in the mixed solution is 0.1mol L -1 -2.0 mol L -1 。
4. The preparation method according to claim 1 or 2, wherein the tin salt is tin tetrachloride pentahydrate.
5. The method according to claim 1 or 2, wherein the carbon source is glucose, fructose or sucrose.
6. The preparation method according to claim 1 or 2, wherein the hydrothermal reaction condition is 90-190 ℃ and the reaction time is 0.5-20 hours.
7. A tin dioxide@carbon composite nanomaterial of coral morphology prepared by the method of any one of claims 1 to 6.
8. The semi-solid negative electrode slurry is characterized in that the tin dioxide and carbon composite nanomaterial with coral morphology as claimed in claim 7 is adopted as an active material.
9. The semi-solid anode slurry according to claim 8, wherein the preparation method of the semi-solid anode slurry comprises the following steps: grinding the coral-shaped tin dioxide@carbon composite nanomaterial and conductive carbon black, dispersing the ground powder in electrolyte under magnetic stirring, adding a high molecular polymer into the dispersed slurry, and continuously stirring to form homogeneous slurry.
10. The semi-solid lithium ion battery is characterized in that the semi-solid lithium ion battery is prepared by adopting the semi-solid negative electrode slurry as claimed in claim 8 or 9.
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