CN110690441B - 3D structure nano tin-based lithium ion battery electrode plate and preparation method thereof - Google Patents
3D structure nano tin-based lithium ion battery electrode plate and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 belongs to the technical field of lithium ion batteries, and particularly relates to a 3D-structure nano tin-based lithium ion battery electrode plate and a preparation method thereof. The electrode plate comprises a current collector and an active material, wherein the current collector is a foam metal material, and the active material is distributed on the surface of the foam metal material and in a porous structure of the foam metal material; the active material is of a core-shell structure, wherein nano tin is used as a core, and graphene is used as a shell. The active material in the electrode slice is a composite material of nano tin and graphene, and has higher theoretical specific capacity; through the limitation of the holes of the graphene coated on the surface of the nano tin and the current collector on the active material, the influence of volume change of the nano tin in the charging and discharging process is effectively relieved, and therefore the circulation stability of the electrode plate is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a 3D-structure nano tin-based lithium ion battery electrode plate and a preparation method thereof.
Background
At present, the commercial lithium ion battery negative electrode materials mainly include carbon materials (such as graphite), silicon materials (such as simple substance silicon), tin materials (such as simple substance tin), and the like. Wherein the graphite has a low lithium intercalation/deintercalation voltage andthe lithium ion battery anode material has rich reserves and low price, and occupies the dominant position of the lithium ion battery anode material for a long time. However, the theoretical specific capacity of the graphite is only 372mAh g-1The theoretical specific capacity of the simple substance tin can reach 994 mAh.g-1Therefore, the tin material used as the negative electrode material has certain advantages in the aspect of improving the specific capacity of the lithium ion battery.
In the prior art, a tin-based negative plate takes elemental tin or tin oxide as a negative active substance and is distributed on the surface of a current collector. However, the negative active material has a large volume change during charging and discharging, and the internal stress of the material is large, so that the pulverization of the tin material and the falling off of the current collector are easily caused, and the cycling stability of the tin-based negative plate is affected.
Disclosure of Invention
The invention aims to provide a 3D structure nano tin-based lithium ion battery electrode plate to solve the problem of poor cycle stability of a tin-based negative electrode plate in the prior art.
The invention also aims to provide a preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery, and the prepared tin-based negative electrode plate has better circulation stability.
The invention also aims to provide the lithium ion battery which has better cycle stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
A3D structure nanometer tin-based lithium ion battery electrode plate comprises a current collector and an active material, wherein the current collector is a foam metal material, and the active material is distributed on the surface of the foam metal material and in a porous structure of the foam metal material; the active material is of a core-shell structure, wherein nano tin is used as a core, and graphene is used as a shell.
The electrode plate of the 3D structure nano tin-based lithium ion battery is a tin-based electrode plate with a 3D structure, and most of the electrode plates are negative electrodes in the lithium ion battery. The active material in the electrode plate is a graphene-coated nano tin material, and due to the fact that graphene has certain toughness, graphene on the surface generates certain constraint force on nano tin when the nano tin expands, and expansion of the nano tin is inhibited; meanwhile, when the nano tin shrinks, the graphene can shrink together with the nano tin, so that the structure of the active material is relatively stable. The current collector is made of foam metal materials, has porosity in the three-dimensional direction and high porosity, and the active materials can be filled in the pores of the current collector, so that the falling of the active materials is effectively prevented, and the stability of a pole piece structure is maintained in the charging and discharging processes; the current collector has a large specific surface area, plays a role in buffering the change of the volume of the active material, and effectively improves the cycle performance of the pole piece. In the pole piece, the foam metal material and the graphene-coated nano tin material are matched for use, so that the problems of volume effect, poor conductivity and the like of the active material can be improved to a great extent, and the cycle performance of the pole piece is further improved.
In order to further enhance the stability of the active material, preferably, the particle size of the nano tin is 10-100 nm, and the thickness of the graphene is 1-5 nm.
The active material in the electrode plate is a tin-carbon composite material, if the content of carbon is high, the specific capacity of the active material is reduced, and the preferred mass ratio of the nano tin to the graphene is (5-20): 1.
The foam metal material used by the electrode plate has a porous structure and is a commercially available product. Generally speaking, the aperture of the foam metal material is 0.1-10 mm, the porosity is above 90%, and the thickness is 2-5 mm, so as to meet the use requirement. Preferably, the foam metal material is foam nickel or foam copper.
The preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery adopts the technical scheme that:
a preparation method of a 3D structure nano tin-based lithium ion battery electrode plate comprises the following steps: taking a foam metal material as a current collector, soaking the foam metal material in slurry containing the nano tin/graphene oxide composite material, taking out, drying, compacting, and calcining in an inert atmosphere to obtain the nano tin/graphene oxide composite material; the nano tin/graphene oxide composite material is of a core-shell structure, wherein nano tin is used as a core, and graphene oxide is used as a shell.
In the preparation method, when the current collector is immersed in the slurry containing the nano tin/graphene oxide composite material, a small amount of the nano tin/graphene oxide composite material is adsorbed to the surface of the current collector, and most of the nano tin/graphene oxide composite material is filled in the porous structure of the current collector. A tablet press is adopted during compaction, the used pressure is about 10MPa, and the nano tin/graphene oxide composite material and the pore structure of the current collector can be in close contact in the compaction process; the compaction also has the advantages of improving the strength of the electrode plate, reducing the thickness of the electrode plate, facilitating the assembly of the battery, increasing the density and the like. During calcination, the calcination is performed in an inert atmosphere (such as nitrogen, argon and the like), graphene is oxidized to form graphene in the calcination process, preferably, the calcination temperature is 500-700 ℃, and the calcination time is 1-3 h. In conclusion, the pole piece with better cycling stability is prepared by a simpler method.
The slurry containing the nano tin/graphene oxide composite material is prepared by the following method:
(1) mixing nano tin, graphene oxide and water, carrying out hydrothermal reaction to obtain nano tin/graphene oxide gel, and carrying out freeze drying on the nano tin/graphene oxide gel to obtain a nano tin/graphene oxide composite material; the mass ratio of the nano tin to the graphene oxide is (5-10) to 1;
(2) and dispersing the crushed nano tin/graphene oxide composite material in water to obtain the nano tin/graphene oxide composite material.
In the preparation method of the slurry, the nano tin and the graphene oxide are dispersed in water, and the amount of the graphene oxide is enough to enable the graphene oxide to form gel in the hydrothermal reaction process and to coat the nano tin in the gel. And (3) directly sublimating and removing water in the gel by freeze drying under the condition of keeping the gel structure, wherein the temperature of the freeze drying is-60 to-40 ℃, and the time is 5-15 hours. In order to uniformly disperse the nano tin/graphene oxide composite material in water, a stirring mode is adopted during dispersion, and the nano tin/graphene oxide composite material is stirred vigorously and fully stirred, so that the nano tin/graphene oxide enters a porous structure of the foam metal material. Preferably, in the step (2), 15-20 mL of water is used per 0.5g of the nano tin/graphene oxide composite material.
The slurry containing the nano tin/graphene oxide composite material can be prepared by adopting the following method: mixing nano tin, graphene oxide and water, and then carrying out hydrothermal reaction to obtain the nano tin oxide graphene oxide film; the mass ratio of the nano tin to the graphene oxide is more than 10:1 and less than or equal to 20: 1. when the nano tin and the graphene oxide in the mass ratio are adopted, the amount of the graphene oxide is relatively small, and a glue solution of the graphene oxide coated with the nano tin is formed in the hydrothermal reaction, so that the operation process is simplified, and a product obtained after the hydrothermal reaction is directly used as slurry.
In order to ensure that the hydrothermal reaction can be carried out and save energy, the temperature of the hydrothermal reaction is 180-200 ℃ and the time is 10-14 h.
The lithium ion battery adopts the technical scheme that:
a lithium ion battery comprises a positive electrode and a negative electrode, wherein the negative electrode is the 3D structure nano tin-based electrode plate.
The cathode of the existing lithium ion battery can be replaced by using the electrode plate of the invention, and then the corresponding lithium ion battery can be obtained. In general, as the positive active material of the lithium ion battery, commonly used lithium nickel oxide, lithium cobalt oxide, lithium manganese oxide, or the like can be used, and as the electrolyte and the separator, commonly used in the prior art can be used. The lithium ion battery of the invention can be a liquid, solid or semi-solid lithium ion battery. The lithium ion battery adopting the electrode plate as the cathode has the advantages of high specific capacity and good cycling stability.
Drawings
FIG. 1 is an SEM image of foam nickel used for a 3D structure nano tin-based lithium ion battery electrode plate of the invention;
fig. 2 is an SEM image of an electrode sheet of example 1 of the present invention;
fig. 3 is a voltage versus capacity curve for a lithium ion battery of example 7 of the present invention;
fig. 4 is a voltage versus capacity curve for a lithium ion battery of example 8 of the present invention;
fig. 5 is a cycle curve of the lithium ion battery of example 9 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The nano tin used in the following examples was prepared by a method comprising the steps of: preparing a tin chloride aqueous solution with the concentration of 0.1mol/L by adopting tin tetrachloride pentahydrate and preparing a sodium borohydride aqueous solution with the concentration of 0.2 mol/L; the aqueous tin chloride solution was placed in a 500mL beaker and 5g of polyethylene glycol 600 was added, and then the beaker was placed on a magnetic stirrer, which was kept at room temperature and stirred slowly. And slowly adding 8mL of 0.2mol/L sodium borohydride solution into the beaker in the stirring process, continuously stirring for 3 hours, wherein a gray precipitate appears in the stirring process, and then carrying out suction filtration, centrifugal washing, drying and grinding to obtain the nano tin, wherein the particle size of the prepared nano tin is 10-100 nm.
The nickel foam used in the following examples is a commercially available product with a thickness of 1.6mm, a pore size of 0.1-1 mm, and a porosity of 98%. The structure of the nickel foam used is shown in FIG. 1.
First, embodiment of electrode plate of 3D structure nano tin-based lithium ion battery
Example 1
The electrode plate of the 3D-structure nano tin-based lithium ion battery comprises a current collector and an active material, wherein the current collector is foamed nickel, and the active material is distributed on the surface of the foamed nickel and in a porous structure; the active material is a composite material with a shell of nano tin and a shell of graphene, wherein the particle size of the nano tin is 10-100 nm, the thickness of the graphene is 1-5 nm, and the mass ratio of the graphene to the nano tin is 1: 5.
example 2
The electrode plate of the 3D-structure nano tin-based lithium ion battery comprises a current collector and an active material, wherein the current collector is foamed nickel, and the active material is distributed on the surface of the foamed nickel and in a porous structure; the active material is a composite material with a shell of nano tin and a shell of graphene, wherein the particle size of the nano tin is 10-100 nm, the thickness of the graphene is 1-5 nm, and the mass ratio of the graphene to the nano tin is 1: 10.
example 3
The electrode plate of the 3D-structure nano tin-based lithium ion battery comprises a current collector and an active material, wherein the current collector is foamed nickel, and the active material is distributed on the surface of the foamed nickel and in a porous structure; the active material is a composite material with a shell of nano tin and a shell of graphene, wherein the particle size of the nano tin is 10-100 nm, the thickness of the graphene is 1-5 nm, and the mass ratio of the graphene to the nano tin is 1: 20.
second, embodiment of preparation method of nano tin-based lithium ion battery electrode plate with 3D structure
Example 4
The preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery comprises the following steps:
(1) dispersing 2g of nano tin and 0.4g of graphene oxide (the mass ratio of the nano tin to the graphene oxide is 5: 1) in 100mL of deionized water, and then carrying out ultrasonic treatment (the ultrasonic frequency is 120kHz, and the ultrasonic time is 2 hours) to obtain a mixed solution; then pouring the mixed solution into a high-pressure reaction kettle, and then placing the reaction kettle in an oven to react for 14 hours at the temperature of 200 ℃ to obtain gel;
(2) transferring the gel into a freeze dryer, and freeze-drying at-60 ℃ for 5h to obtain a composite material;
(3) dispersing 0.5g of the crushed composite material in 15mL of water to obtain slurry, soaking foamed nickel with the diameter of 14-18 mm in the slurry for 20min, and stirring in the soaking process; and then taking out and drying, pressing for 1-2 s on a tablet press by adopting 10Mpa, and then calcining for 3h at 700 ℃ in an argon atmosphere to obtain the electrode plate in the embodiment 1.
Example 5
The preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery comprises the following steps:
(1) dispersing 2g of nano tin and 0.2g of graphene oxide (the mass ratio of the nano tin to the graphene oxide is 10: 1) in 100mL of deionized water, and then carrying out ultrasonic treatment (the ultrasonic frequency is 80kHz, and the ultrasonic time is 2.5 hours) to obtain a mixed solution; then pouring the mixed solution into a high-pressure reaction kettle, and then placing the reaction kettle in an oven to react for 14 hours at the temperature of 200 ℃ to obtain gel;
(2) transferring the gel into a freeze dryer, and freeze-drying at-50 ℃ for 10h to obtain a composite material;
(3) and (2) dispersing 0.5g of the crushed composite material in 15mL of water to obtain slurry, then soaking the foamed nickel with the size of 14-18 mm in the slurry for 30min, stirring in the soaking process, taking out and drying, pressing for 1-2 s on a tablet press under the pressure of 10Mpa, and then calcining for 2h at the temperature of 600 ℃ in the argon atmosphere to obtain the electrode slice of the embodiment 2.
Example 6
The preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery comprises the following steps:
(1) dispersing 2g of nano tin and 0.1g of graphene oxide (the mass ratio of the nano tin to the graphene oxide is 20: 1) in 100mL of deionized water, and then carrying out ultrasonic treatment (the ultrasonic frequency is 100kHz, and the ultrasonic time is 1h) to obtain a mixed solution; then pouring the mixed solution into a high-pressure reaction kettle, and then placing the reaction kettle in an oven to react for 14 hours at 180 ℃ to obtain a glue solution of nano tin/graphene oxide;
(3) soaking foamed nickel with the size of 14-18 mm in the glue solution of nano tin/graphene oxide for 20min, stirring in the soaking process, taking out and drying, pressing for 1-2 s on a tablet press under the pressure of 10Mpa, and calcining for 2h at the temperature of 600 ℃ in the argon atmosphere to obtain the electrode plate of the embodiment 3.
Embodiments of the lithium ion Battery
Example 7
In the lithium ion battery of the present example, the electrode sheet of example 1 was used as a working electrode, a lithium sheet was used as a counter electrode, lithium salt in the electrolyte was lithium hexafluorophosphate, the solvent was a mixture of PC/EC/DEC, and the separator was polytetrafluoroethylene, and the working electrode, the counter electrode, the electrolyte, and the separator were assembled into a half-cell.
Examples 8 to 9
The structures of the lithium ion batteries of examples 8 to 9 were as described in example 7, except that: the working electrode in example 8 was the electrode sheet in example 2, and the working electrode in example 9 was the electrode sheet in example 3.
In other embodiments of the lithium ion battery, the electrode sheet of embodiment 1 may be used to replace the existing tin-based negative electrode, and based on the advantage of the tin-based electrode sheet in terms of cycle stability, the cycle stability of the corresponding lithium ion battery may be improved.
Test example 1
The electrode sheet of example 1 was subjected to SEM test, and the test results are shown in fig. 2. As can be seen from fig. 1 and 2, the active material is distributed in the pores of the nickel foam, and the nickel foam and the active material are tightly bonded.
Test example 2
The lithium ion batteries of examples 7 to 9 were subjected to a performance test using a blue battery test system (blue electronic corporation, wuhan). The test results are shown in FIGS. 3 to 5. As can be seen from fig. 3 to 5, the lithium ion battery of the present invention has good cycling stability and high coulombic efficiency.
Claims (10)
1. The electrode plate of the 3D structure nano tin-based lithium ion battery is characterized by comprising a current collector and an active material, wherein the current collector is a foam metal material, and the active material is distributed on the surface of the foam metal material and in a porous structure of the foam metal material; the active material is of a core-shell structure, wherein nano tin is used as a core, and graphene is used as a shell; the electrode plate of the 3D structure nano tin-based lithium ion battery is prepared by the following steps: taking a foam metal material as a current collector, soaking the foam metal material in slurry containing the nano tin/graphene oxide composite material, taking out, drying, compacting, and calcining in an inert atmosphere to obtain the nano tin/graphene oxide composite material; the nano tin/graphene oxide composite material is of a core-shell structure, wherein nano tin is used as a core, and graphene oxide is used as a shell; the slurry containing the nano tin/graphene oxide composite material is prepared by the following method:
(1) mixing nano tin, graphene oxide and water, carrying out hydrothermal reaction to obtain nano tin/graphene oxide gel, and carrying out freeze drying on the nano tin/graphene oxide gel to obtain a nano tin/graphene oxide composite material; the mass ratio of the nano tin to the graphene oxide is (5-10) to 1;
(2) and dispersing the crushed nano tin/graphene oxide composite material in water to obtain the nano tin/graphene oxide composite material.
2. The electrode plate of the 3D structure nano tin-based lithium ion battery of claim 1, wherein the nano tin has a particle size of 10-100 nm and a graphene thickness of 1-5 nm.
3. The electrode plate of the 3D structure nano tin-based lithium ion battery as claimed in claim 1, wherein the mass ratio of the nano tin to the graphene is (5-20): 1.
4. The electrode plate of the 3D structure nano tin-based lithium ion battery according to any one of claims 1 to 3, wherein the foam metal material is foam nickel or foam copper.
5. A preparation method of a 3D structure nano tin-based lithium ion battery electrode plate is characterized by comprising the following steps: taking a foam metal material as a current collector, soaking the foam metal material in slurry containing the nano tin/graphene oxide composite material, taking out, drying, compacting, and calcining in an inert atmosphere to obtain the nano tin/graphene oxide composite material; the nano tin/graphene oxide composite material is of a core-shell structure, wherein nano tin is used as a core, and graphene oxide is used as a shell; the slurry containing the nano tin/graphene oxide composite material is prepared by the following method:
(1) mixing nano tin, graphene oxide and water, carrying out hydrothermal reaction to obtain nano tin/graphene oxide gel, and carrying out freeze drying on the nano tin/graphene oxide gel to obtain a nano tin/graphene oxide composite material; the mass ratio of the nano tin to the graphene oxide is (5-10) to 1;
(2) and dispersing the crushed nano tin/graphene oxide composite material in water to obtain the nano tin/graphene oxide composite material.
6. The preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery according to claim 5, wherein the calcining temperature is 500-700 ℃ and the calcining time is 1-3 h.
7. The preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery as claimed in claim 5, wherein in the step (2), 15-20 mL of water is used per 0.5g of nano tin/graphene oxide composite material.
8. The preparation method of the electrode plate of the 3D-structure nano-tin-based lithium ion battery according to claim 5, wherein the slurry containing the nano-tin/graphene oxide composite material is prepared by the following method: mixing nano tin, graphene oxide and water, and then carrying out hydrothermal reaction to obtain the nano tin oxide graphene oxide film; the mass ratio of the nano tin to the graphene oxide is more than 10:1 and less than or equal to 20: 1.
9. the preparation method of the electrode plate of the 3D structure nano tin-based lithium ion battery according to any one of claims 5 to 8, wherein the temperature of the hydrothermal reaction is 180-200 ℃ and the time is 10-14 h.
10. A lithium ion battery is characterized by comprising a positive electrode and a negative electrode, wherein the negative electrode is the electrode plate of the 3D structure nano tin-based lithium ion battery as claimed in any one of claims 1 to 4.
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