CN114551833A - Coral-shaped tin dioxide @ carbon composite nanomaterial and preparation method thereof, semi-solid negative electrode slurry and semi-solid lithium ion battery - Google Patents
Coral-shaped 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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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
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- 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
- 239000008103 glucose Substances 0.000 claims description 2
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- 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 2
- 238000000576 coating method Methods 0.000 abstract description 7
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/366—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-shaped tin dioxide @ carbon composite nanomaterial, a preparation method thereof, semi-solid negative electrode slurry and a semi-solid lithium ion battery. Meanwhile, when the semi-solid lithium ion battery slurry is prepared, polyvinylidene fluoride is added as an additive, so that the formed semi-solid 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 beneficial to large-scale production and research and development of novel electrode materials, and the characteristic of no current collector can avoid capacity attenuation caused by the fact that active materials form cracks and 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, belongs to the technical field of semi-solid rechargeable batteries, and particularly relates to a coral-shaped tin dioxide @ carbon composite nanomaterial and a preparation method thereof, battery negative electrode slurry and a semi-solid lithium ion battery.
Background
The negative electrode of the current commercial lithium ion battery is graphite, and the problems of more side reactions, poor rate performance and the like caused by low capacity, poor stability and low purity of the graphite make people urgently need to find a material which has a stable structure and high capacity and can adapt to high-current density charge and discharge and is used for replacing natural graphite as the negative electrode of the rechargeable lithium ion battery.
Among numerous materials, tin dioxide can be used as a substitute material for the next generation of lithium ion battery cathode due to the advantages of low production cost, simple preparation process, stable structure, adaptability to large-current charge and discharge and the like. Most of the current preparation processes of the negative electrode material are coating methods, the prepared material and conductive carbon black are ground and dispersed in N-methyl pyrrolidone to form slurry, then the slurry is coated on a current collector copper foil in a certain thickness, and hot rolling and slicing are carried out after drying to obtain a negative electrode plate. The complex electrode plate 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 plate become more, and the research and development and preparation cost of the electrode are greatly improved. In addition, in the circulating process of the electrode plate, the surface of the electrode plate is cracked due to the volume expansion of the material in the charging and discharging processes, so that the electrode material falls off 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 nano material 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 low in cost.
The invention also aims to provide semi-solid anode 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 commercialized graphite anode.
The invention finally aims to provide a semi-solid lithium ion battery, which is prepared by using the coral-shaped tin dioxide @ carbon composite nanomaterial as semi-solid cathode slurry of an active material, wherein the semi-solid cathode slurry does not need a current collector, has higher capacity, and can prevent an electrode plate from cracking and falling off the current collector in a circulation process, so that the semi-solid lithium ion battery has the characteristic of high stability. The semi-solid lithium ion battery with novelty, high capacity, low cost and good stability is obtained.
The specific technical scheme of the invention is as follows:
the preparation method of the coral-shaped tin dioxide @ carbon composite nano material comprises the following specific steps:
dissolving tin salt 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 the coralline tin dioxide @ carbon composite material.
The molar ratio of the carbon source to the tin salt is 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-1Preferably 0.25mol L-1(ii) a The concentration of the carbon source in water is 0.1-2.0mol L-1Preferably 0.5mol L-1；
Further, the tin salt is stannic chloride pentahydrate (SnCl)4·5H2O); the carbon source is glucose, fructose or sucrose.
The hydrothermal reaction is carried out under the conditions of 90-190 ℃ and the reaction time is 0.5-20 hours.
The coral-shaped tin dioxide @ carbon composite nanomaterial provided by the invention is prepared by the method, the length range of the composite nanomaterial is 1.0-3.0 mu m, the coral-shaped tube diameter is 300-400nm, the exterior of the composite nanomaterial is a tin dioxide shell, and amorphous carbon particles are wrapped inside the composite nanomaterial.
In the preparation method of the coral-shaped tin dioxide @ carbon nano composite material, provided by the invention, tin tetrachloride pentahydrate (SnCl) is used4·5H2O) is used as tin salt, cane sugar is used as a carbon source, the one-step hydrothermal reaction is carried out in deionized water, and the coral-shaped tin dioxide and carbon composite is obtained after washing and drying. Under the condition of heating, the stannic chloride is hydrolyzedWherein Sn is4+Combined with hydroxide radical in water to form Sn (OH)4Which is oxidized to dehydrate sucrose into carbon particles and thus encapsulated in Sn (OH)4In the formation of microspheres, with the progress of the reaction, coated with carbon Sn (OH)4Fusing with each other, gradually growing outward to a bent structure, and finally coating Sn (OH) with the outer layer along with mutual dehydration reaction between hydroxyl groups4Gradually turns into tin dioxide and tightly wraps the carbon inside. The prepared tin dioxide @ carbon composite material is used as the negative electrode of the lithium ion battery, so that the conductivity of tin dioxide can be improved, and the tin dioxide has excellent stability due to the 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 nano material and conductive carbon black, dispersing the ground powder in an electrolyte under magnetic stirring, adding a high-molecular polymer into the dispersed slurry, and continuing stirring to form homogeneous slurry;
the mass ratio of the coral-shaped tin dioxide @ carbon composite nano material to the conductive carbon black is 1: 4-8: 1, preferably 2:1, and the mass-to-volume ratio of the coral-shaped tin dioxide @ carbon composite nano material to the electrolyte is 1: 20-1: 5g mL-1Preferably 1:10g mL-1。
The electrolyte is a binary electrolyte prepared by mixing LiPF6Dissolved in a solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) mixed in equal volumes, LiPF6The concentration is 1.0M; the electrolyte acts as a dispersant for the solid powder.
The added high molecular polymer is PVDF, and the ratio of the mass of the PVDF to the mass of the coral-shaped tin dioxide @ carbon composite nano material is 1: 10-1: 2, preferably 1: 4.
And the time for continuously stirring is 2-24 h.
The semi-solid lithium ion battery provided by the invention is prepared by adopting the semi-solid cathode slurry.
Compared with the traditional solid electrode, the semisolid 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 processes and procedures are greatly reduced, capacity attenuation caused by the fact that the electrode material falls off from a current collector is avoided, and compared with the traditional electrode, the semisolid electrode does not generate cracks in the charging and discharging processes, and the cycle life can be 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 under the influence of gravity along with the stopping of stirring, so the high molecular polymer added in the invention can be dissolved in the environment of electrolyte to form a frame, a conductive network is formed, and the active material is prevented from being precipitated. When the active material expands in volume during charging and discharging, the active material is dispersed in the electrolyte, so that compared with the traditional electrode, the active material does not generate cracks to enable capacity to be attenuated, fast electron ion transmission is facilitated, and the performance of the battery can be improved.
The tin salt is used as a raw material, sucrose is used as a carbon source, and the tin salt is synthesized by a one-step hydrothermal method and used as a lithium ion battery cathode. Meanwhile, when the semi-solid lithium ion battery slurry is prepared, PVDF is added as an additive, so that the formed semi-solid 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 beneficial to large-scale production and research and development of novel electrode materials, and the characteristic of no current collector can avoid capacity attenuation caused by the fact that active materials form cracks and 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 composite material are gradually fused along with the reaction, and the carbon cores are combined in a non-chemical bond mode in a contact mode, loose carbon is arranged inside the prepared tin dioxide @ carbon composite material, and the integral conductivity of the material is improved;
(2) the prepared tin dioxide @ carbon anode material is applied to a lithium ion battery anode and shows higher specific capacity and more excellent capacity reversibility;
(3) the use of the semi-solid slurry electrode can avoid the falling of active substances caused by the volume expansion of materials in the charging and discharging processes, is favorable for regulating and controlling the content of the active substances in the battery, and is favorable for the research and development of the materials and the reduction of the process cost of the battery;
(4) the raw materials are low in price, the preparation process is simple, and large-scale production can be carried out.
Drawings
FIG. 1 is an XRD pattern of coral-like tin dioxide @ carbon prepared in example 1;
FIG. 2 is an SEM image of coral-like tin dioxide @ carbon prepared in example 1;
FIG. 3 is a TEM image of coral-like tin dioxide @ carbon prepared in example 1;
FIG. 4 is a TGA plot of coral-like 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 of the cycle performance of the semi-solid slurry lithium ion battery of example 4;
FIG. 7 is a graph showing the charge and discharge curves of the semi-solid slurry lithium ion battery of example 4;
FIG. 8 is a graph of rate performance of the semi-solid slurry lithium ion battery of example 4;
FIG. 9 is a graph showing cycle performance of the electrode sheet lithium ion battery in comparative example 1;
fig. 10 is a graph showing charge and discharge curves of the electrode sheet lithium ion battery in comparative example 1.
Detailed Description
The invention will be described in detail below with reference to the following examples and the accompanying drawings.
Example 1
The preparation method of the coral-shaped tin dioxide @ carbon composite nano material comprises the following specific steps:
weighing 10mmol of SnCl4·5H2Adding 40mL of deionized water into a beaker, magnetically stirring to dissolve the deionized water, adding 20mmol of sucrose, transferring the mixed solution into a 50mL polytetrafluoroethylene reaction kettle liner after the sucrose is completely dissolved, and reacting for 6 hours at 180 ℃; after the reaction is finished, respectively using water and absolute ethyl alcohol to carry out centrifugal washing, wherein the rotating speed of a centrifugal machine per minute is 6000 revolutions, 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 FIG. 1, from which it can be seen that the prepared nano composite material is composed of tin dioxide, and the carbon wrapped inside is difficult to observe from the figure; the SEM image is shown in fig. 2, and it can be seen that the prepared tin dioxide @ carbon nanocomposite material exhibits a winding coral shape; FIG. 3 is a TEM image of a tin dioxide @ carbon composite, from which it can be known that the prepared composite is a solid structure and the diameter of the prepared coral-shaped whisker is about 400 nm; the thermogravimetric curve in fig. 4 shows that the carbon content in the composite material is 56%.
Example 2
Preparation of a coral-based tin dioxide @ carbon electrode plate and application of the electrode plate as a lithium battery negative electrode material, comprising the following steps of:
(1) preparation of slurry: uniformly mixing the prepared tin dioxide @ carbon nanocomposite, conductive carbon black and CMC in a ratio of 7:2:1 or 8:1:1, adding a proper amount of SBR with water as a dispersing agent, and magnetically stirring for 8-12 hours to form uniform slurry.
(2) And coating the stirred slurry on a clean copper foil in a certain thickness by a coating method, drying the copper foil for 8 to 12 hours in a vacuum drying oven at the temperature of between 60 and 80 ℃, and cutting the copper foil into small wafer electrodes with certain sizes by using a cutting machine.
(3) The prepared electrode slice is assembled into a 2032 type button cell in a glove box (the water value and the oxygen value are less than or equal to 0.01ppm) filled with high-purity argon. Mixing LiPF6Dissolved in a solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) mixed in equal volumes, LiPF6The concentration was 1.0M, thereby preparing an electrolyte. The specific method for assembling the battery comprises the following steps: dropping a drop of electrolyte on the electrode shell and placing the electrode slice (the small electrode slice)Wafer electrode), then two drops of electrolyte are dripped to wet the surface of the electrode, a piece of Celgard diaphragm is placed on the electrode piece, a drop of electrolyte is dripped on the diaphragm, then a lithium piece is placed as a counter electrode, then a gasket and an elastic piece are placed as supports, and the battery is tightly packaged by a hydraulic press.
Example 3
A preparation method of semi-solid electrode slurry comprises the following specific steps: grinding and mixing 0.1g of the prepared coralline tin dioxide @ carbon nano composite material and 0.05g of conductive carbon black, then magnetically stirring and dispersing the uniformly ground sample in 1mL of the electrolyte in a glove box, adding 0.025g of PVDF after uniform stirring and dispersion, 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 homogeneity, and it can be seen from the rightmost graph in fig. 5 that it is not delaminated after standing for 48 hours.
Preparation of a semi-solid lithium ion battery: and directly dripping the prepared semi-solid electrode slurry on an electrode shell, and calculating the content of the active material in the battery according to the mass difference before and after the electrode shell is dripped with the slurry. Then covering a piece of glass fiber soaked by binary electrolyte as a diaphragm, then placing a piece of lithium as a counter electrode, then placing a gasket and a spring plate as supports, placing a battery cathode shell, and then pressing the battery on a hydraulic press.
Example 4
And (3) testing the electrochemical performance of the semi-solid lithium ion battery:
the semi-solid lithium ion battery assembled in the embodiment 3 is placed for 8 to 12 hours and then placed at 0.1A g-1The results of the cycle performance and the charge/discharge performance test of (1) were shown in fig. 6 and 7, and it can be seen that the capacity of the battery can be stabilized at 528mAh g after 100 cycles-1Left and right, as can be seen from fig. 7, there is a platform around 1.0V on the discharge curve, the second platform is around 0.5V; for the charging process, there is a plateau around 0.7V and 1.3V, respectively.
The rate capability of the battery is tested at the same time, and the set current density gradient is 0.1A g-1～1.0A g-1. The graph of the measured rate performance is shown in fig. 8, and the graph shows that the prepared semi-solid lithium ion battery is 0.1A g-1Shows 804mAh g at a current density of-1Even at 1.0A g-1Can still show 165mAh g under the high current density-1And back to 0.1A g again-1The current density of the battery can still show 771mAh g-1The stable capacity of (a) indicates that it is well adapted to large current charging and discharging, and the result is shown in fig. 8.
Comparative example 1
Testing the electrochemical performance of the electrode plate lithium ion battery:
the battery assembled in example 2 was left for 8 to 12 hours and then placed at 0.1A g-1The current density of the battery is measured, and the results are shown in fig. 9 and 10, which also show excellent electrochemical performance, because the solid electrode can not relieve the volume expansion of the material in the charging and discharging process, the material falls off from the electrode, so that only 150.6mAh g is remained after 100 cycles-1The capacity of (c).
The semi-solid battery is not a traditional electrode plate battery, so that the electrode plate is not cracked and falls off from the current collector due to volume expansion of materials in the charging and discharging processes, and the capacity is irreversibly reduced, and comparison between fig. 7 and fig. 10 shows that the semi-solid electrode has the same charging and discharging curve as the traditional electrode, and the charging and discharging curve of the battery is not changed due to the semi-solid battery, and the platform of the charging and discharging curve is not changed.
The detailed description of a new type of tin dioxide @ carbon nanocomposite material with coral morphology and the preparation method thereof, a rechargeable lithium ion battery and a semi-solid lithium ion battery and the preparation technology thereof, which are provided above with reference to the embodiments, are illustrative and not restrictive, and several embodiments can be cited within the scope of the present invention, so that variations and modifications thereof without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the coral-shaped tin dioxide @ carbon composite nanomaterial is characterized by comprising the following steps of:
dissolving tin salt 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 the coralline tin dioxide @ carbon composite material.
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-1-2.0mol L-1。
4. The method according to claim 1 or 2, characterized in that 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 method according to claim 1 or 2, wherein the hydrothermal reaction is carried out under 90 to 190 ℃ for 0.5 to 20 hours.
7. Tin dioxide @ carbon composite nanomaterial with coral morphology prepared by the preparation method of any one of claims 1-7.
8. The semi-solid negative electrode slurry is characterized by being prepared by adopting a coral-shaped tin dioxide @ carbon composite nano material as an active material.
9. The semi-solid anode slurry according to claim 8, wherein the semi-solid anode slurry is prepared by a method comprising: grinding the coral-shaped tin dioxide @ carbon composite nano material and conductive carbon black, dispersing the ground powder in an electrolyte under magnetic stirring, adding a high-molecular polymer into the dispersed slurry, and continuing stirring to form homogeneous slurry.
10. A semi-solid lithium ion battery prepared using the semi-solid negative electrode slurry of claim 8 or 9.
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