CN110911688A - High-safety lithium ion battery cathode composite material and preparation method thereof - Google Patents
High-safety lithium ion battery cathode composite material and preparation method thereof Download PDFInfo
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- 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
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- 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
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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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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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high-safety lithium ion battery negative electrode composite material and a preparation method thereof, wherein the negative electrode composite material comprises a core and a coating layer coated outside the core, the core is graphite, the coating layer is a thermal denaturation composite material, and the thickness of the coating layer is 0.5-1 mu m. The surface of the material is coated with the thermal denaturation material, and the smooth reciprocating penetration of lithium ions can be ensured by utilizing the melting point or softening point of the thermal denaturation material at normal temperature and the pores among the particles without influencing the internal resistance and the rate charge-discharge efficiency of the battery, when the temperature of the battery rises, the thermal denaturation material is melted or swelled in a short time, the pores among the particles are rapidly reduced or disappeared, the thermal shutoff effect is realized, the lithium ion transmission channel is cut off, the thermal runaway of the battery is prevented, and the safety performance of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery materials, in particular to a high-safety lithium ion battery cathode composite material and a preparation method thereof.
Background
With the increasing demand of the market for high specific energy density lithium ion batteries, the lithium ion batteries are required to have high specific energy density and long cycle life on the premise of ensuring the safety performance of the batteries. The negative electrode material is a key factor influencing the safety performance and energy density of the lithium ion battery, the graphite is mainly used as the current marketable negative electrode material, and although the graphite material is a preferred material of the lithium ion battery due to the advantages of low price, high stability, excellent cycle performance and the like, the lithium ion battery is easy to cause lithium precipitation and thermal runaway in the overcharging process, so that potential safety hazards are caused. At present, the safety measures for improving the graphite cathode material are mainly to coat hard carbon, soft carbon and functional materials thereof on the surface of the material to improve the intercalation rate and heat dissipation performance of lithium ions in the quick charging process, avoid local thermal runaway of the material and improve the safety performance of the material. For example, patent CN 105390678A discloses a negative electrode material and a lithium ion battery comprising the same, wherein the negative electrode material comprises a substrate and a coating layer located on the surface of the substrate, the substrate is a negative electrode active material, the coating layer comprises at least one selected from PEDOT and PSS, and after the negative electrode material is applied to the lithium ion battery, the safety performance, the high-temperature storage performance, the high-temperature cycle performance and the excellent rate performance of the lithium ion battery are improved, but when the material is thermally out of control at an excessively high temperature, the heat dissipation performance deviation of the material cannot realize the self-closing function of the material, so that the safety performance deviation is caused.
Disclosure of Invention
The invention provides a high-safety lithium ion battery cathode composite material and a preparation method thereof for solving the technical problems.
The invention is realized by the following technical scheme:
the high-safety lithium ion battery cathode composite material comprises an inner core and a coating layer coated outside the inner core, wherein the inner core is graphite, and the coating layer is made of a thermal denaturation composite material and is 0.5-1 mu m in thickness. According to the scheme, the surface of the material is coated with the thermal denaturation material, and the smooth reciprocating penetration of lithium ions can be ensured by utilizing the melting point or softening point of the thermal denaturation material at normal temperature and the pores among the particles without influencing the internal resistance and the rate charge-discharge efficiency of the battery, when the temperature of the battery rises, the thermal denaturation material is melted or swelled in a short time, the pores among the particles are rapidly reduced or disappeared, the thermal shutoff effect is realized, the lithium ion transmission channel is cut off, the thermal runaway of the battery is prevented, and the safety performance of the lithium ion battery is improved.
Preferably, the heat-denatured composite material comprises the following components in parts by weight: 50-60 parts of thermal denaturation material, 1-5 parts of aminated graphene, 0.5-2 parts of functional additive and 40-50 parts of binder.
Further, the functional additive comprises the following components in parts by weight: 60-80 parts of ammonium benzene sulfonate and 20-40 parts of ethylene glycol monobutyl ether.
A preparation method of a high-safety lithium ion battery cathode composite material comprises the following steps:
A. preparing a heat-denatured composite material coating liquid;
B. weighing 100-200 parts of graphite with the particle size of 5-10 mu m, adding the graphite into a coating liquid, uniformly dispersing the graphite in a ball mill, drying, crushing and grading to obtain a graphite composite material, transferring the graphite composite material into a tube furnace, introducing inert gas, discharging the gas in the tube, introducing SO2 gas, heating to 100-300 ℃, keeping the pressure in the tube at 1-1.2 Mpa, and keeping the temperature for 1-6 hours; stopping introducing the SO2 gas, introducing the inert gas, and naturally cooling to room temperature to obtain the coated graphite composite material. According to the scheme, aminated graphene is added into the thermal denaturation composite material, and SO is introduced during preparation2Gas at SO2The sulfhydrylation graphene is generated under the action of the organic silicon compound, a network structure is formed, the structural stability of the material is improved, and meanwhile, the electronic conductivity of the material is improved by means of the high specific surface area and the conductivity of the graphene. Meanwhile, the organic ammonium salt in the functional additive can inhibit Li in the film forming process2O is generated, a low-impedance compact SEI film is formed on the surface of the graphite to prevent the further reaction of the negative electrode material and the electrolyte, and simultaneously ethylene glycol monobutyl ether absorbs trace HF generated in the charge-discharge process and enables the HF to be absorbedEthers are decomposed, a compact SEI film is formed on the surface of the negative electrode material, and the contact probability of the material and the electrolyte is reduced, so that the occurrence probability of side reactions and the gas yield of the side reactions are reduced, and the safety performance of the side reactions is improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the surface of the material is coated with the thermal denaturation material, and the smooth reciprocating penetration of lithium ions can be ensured by utilizing the melting point or softening point of the thermal denaturation material at normal temperature and the pores among the particles without influencing the internal resistance and the rate charge-discharge efficiency of the battery, when the temperature of the battery rises, the thermal denaturation material is melted or swelled in a short time, the pores among the particles are rapidly reduced or disappeared, the thermal shutoff effect is realized, the lithium ion transmission channel is cut off, the thermal runaway of the battery is prevented, and the safety performance of the lithium ion battery is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention.
Fig. 1 is an SEM image of the graphite composite material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
The high-safety lithium ion battery cathode composite material comprises a core and a coating layer coated outside the core, wherein the core is graphite, the coating layer is a thermal denaturation composite material, and the thickness of the coating layer is 0.5-1 mu m. The thickness of the coating layer is too thin, when the thermal denaturation material is melted or swelled, the pores among the particles cannot be effectively reduced or disappeared, the thermal shutdown effect cannot be realized, the thermal runaway of the battery cannot be prevented, and the safety performance of the lithium ion battery is not favorable; the coating layer is too thick, when the thermal denaturation material is melted or swelled, the pore energy among particles disappears rapidly, the thermal shutdown effect can be realized, the thermal runaway of the battery is effectively prevented, but the coating layer is an insulating material and does not have any reaction to lithium ions, the capacity exertion of the negative electrode material can be directly influenced by the too thick coating layer, the too thick coating layer can cause particle agglomeration and granulation, the structure is changed, and the characteristics are changed. In order to enhance the performance of the negative electrode composite material, the thickness is 0.5-1 mu m.
Specifically, the thermal denaturation composite material comprises the following components in parts by weight: 50-60 parts of thermal denaturation material, 1-5 parts of aminated graphene, 0.5-2 parts of functional additive and 40-50 parts of binder. Wherein, the thermal denaturation material is one or more of ethylene-vinyl acetate copolymer, polymethyl methacrylate, polystyrene and polyacrylate. The binder is one or more of polyvinyl alcohol, sodium carboxymethylcellulose, styrene butadiene rubber, polyacrylate, polyacrylonitrile and polyacrylamide. The amino content in the aminated graphene is 0.1-5%. The functional additive comprises the following components in parts by weight: 60-80 parts of ammonium benzene sulfonate and 20-40 parts of ethylene glycol monobutyl ether.
The preparation method comprises the following steps:
A. preparing a heat-denatured composite material coating liquid: adding 40-50 parts of binder into 100 parts of N-methyl pyrrolidone organic solvent, uniformly stirring, adding 50-60 parts of thermal denaturation material, uniformly dissolving, adding 1-5 parts of aminated graphene and 0.5-2 parts of functional additive, and uniformly dispersing by ultrasonic to obtain uniform coating liquid.
B. Weighing 100-200 parts of graphite with the particle size of 5-10 mu m, adding the graphite into a coating liquid, uniformly dispersing the graphite in a ball mill, drying, crushing and grading to obtain a graphite composite material, transferring the graphite composite material into a tube furnace, introducing inert gas, discharging the gas in the tube, introducing SO2 gas, heating to 100-300 ℃, keeping the pressure in the tube at 1-1.2 Mpa, and keeping the temperature for 1-6 hours; stopping introducing the SO2 gas, introducing the inert gas, and naturally cooling to room temperature to obtain the coated graphite composite material.
Example 2
Based on the structure and composition of the above embodiments, the present embodiment discloses a specific example.
A. Preparing a heat-denatured composite material coating liquid: adding 45g of polyvinyl alcohol into 100g of N-methylpyrrolidone organic solvent, stirring uniformly, adding 55g of ethylene-vinyl acetate copolymer, dissolving uniformly, adding 3g of aminated graphene, 0.7g of ammonium benzenesulfonate and 0.3g of ethylene glycol monobutyl ether, and dispersing uniformly by ultrasonic to obtain a uniform coating solution.
B. Weighing small-particle-size artificial graphite with the particle size of 8 mu m and 150g, adding the small-particle-size artificial graphite into the coating liquid A, uniformly dispersing the small-particle-size artificial graphite in a ball mill, drying, crushing and grading to obtain a small-particle-size graphite composite material, transferring the composite material B into a tube furnace, firstly introducing argon gas to discharge gas in the tube furnace, and then introducing SO2The flow rate of the gas is 2ml/min, the temperature is raised to 200 ℃, the pressure in the pipe is kept at 1.1Mpa, the heat preservation time is 3 hours, and then the SO is stopped to be introduced2Introducing argon gas into the gas, and naturally cooling to room temperature to obtain the coated graphite composite material. An SEM image of the graphite composite material prepared by the method is shown in figure 1, and it can be seen from the SEM image that the material is in a spherical structure, and the particle size is 5-15 mu m.
Example 3
This example discloses a specific example based on the structure and composition of example 1.
A. Preparing a heat-denatured composite material coating liquid: adding 40g of polyvinyl alcohol into 100g of N-methylpyrrolidone organic solvent, stirring uniformly, adding 60g of ethylene-vinyl acetate copolymer, dissolving uniformly, adding 1g of aminated graphene, 0.3g of ammonium benzenesulfonate and 0.2g of ethylene glycol monobutyl ether, and dispersing uniformly by ultrasonic to obtain a uniform coating solution.
B. Weighing 100g of small-particle-size artificial graphite with the particle size of 5 mu m, adding the small-particle-size artificial graphite into the coating liquid A, uniformly dispersing the small-particle-size artificial graphite in a ball mill, drying, crushing and grading to obtain a small-particle-size graphite composite material, transferring the composite material B into a tube furnace, firstly introducing argon gas to discharge gas in the tube furnace, and then introducing SO2Gas with flow rate of 10ml/min, heating to 100 deg.C, maintaining pressure in the tube at 1.2MPa, and maintaining the temperature for a period of time1h, then stopping the SO introduction2Introducing argon gas into the gas, and naturally cooling to room temperature to obtain the coated graphite composite material.
Example 4
This example discloses a specific example based on the structure and composition of example 1.
A. Preparing a heat-denatured composite material coating liquid: adding 50g of polyvinyl alcohol into 100g of N-methylpyrrolidone organic solvent, stirring uniformly, adding 60g of ethylene-vinyl acetate copolymer, dissolving uniformly, adding 5g of aminated graphene, 1.6g of ammonium benzenesulfonate and 0.4g of ethylene glycol monobutyl ether, and dispersing uniformly by ultrasonic to obtain a uniform coating solution.
B. Weighing small-particle-size artificial graphite with the particle size of 10 mu m and 200g, adding the small-particle-size artificial graphite into the coating liquid A, uniformly dispersing the small-particle-size artificial graphite in a ball mill, drying, crushing and grading to obtain a small-particle-size graphite composite material, transferring the composite material B into a tube furnace, firstly introducing argon gas to discharge gas in the tube furnace, and then introducing SO2Gas with the flow rate of 10ml/min, heating to 300 ℃, keeping the pressure in the pipe at 1Mpa for 6h, and stopping introducing SO2Introducing argon gas into the gas, and naturally cooling to room temperature to obtain the coated graphite composite material.
An artificial graphite having a model number of CP5-M and a particle size of 8 μ M, manufactured by Shanghai fir Co., Ltd, in the market was used as a comparative example, and an experiment was performed with the negative electrode composite material for a battery manufactured by the method of the above example 2-4.
Electricity withholding test
Respectively assembling the lithium ion battery negative electrode materials obtained in the examples 2-4 and the comparative example into button batteries A1, A2, A3 and B1; the preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the copper foil to obtain the copper-clad laminate. The binder is LA132 binder, the conductive agent SP, the negative electrode material is the negative electrode material prepared in the embodiment 2-4, the solvent is secondary distilled water, and the proportion is as follows: and (3) anode material: SP: LA 132: double distilled water =95 g: 1 g: 4 g: 220 mL; the electrolyte is LiPF6/EC + DEC (1: 1), the metal lithium sheet is a counter electrode, the diaphragm is a Polyethylene (PE), polypropylene (PP) or polyethylene propylene (PEP) composite film, the simulated battery is assembled in an argon-filled glove box, the electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.005V-2.0V, and the charging and discharging rate is 0.1C. See table 1 for details:
TABLE 1 comparison of the Power-on test for examples and comparative examples
As can be seen from Table 1, the discharge capacity and the first efficiency of the discharge cells adopting the negative electrode materials obtained in examples 2-4 are obviously higher than those of the comparative examples. Experimental results show that the modified negative electrode material has higher discharge capacity and efficiency, and the specific capacity and the first efficiency of the material are improved because the graphene is coated on the surface of the graphite to improve the conductivity of the material.
Laminate polymer battery fabrication and testing
Then, the cathodes prepared in examples 2 to 4 and the comparative example were used as cathode plates, the plate prepared from lithium iron phosphate was used as an anode plate, LiPF6/EC + DEC (volume ratio 1:1, concentration 1.0 mol/L) was used as electrolyte, and Celgard 2400 film was used as separator, to prepare 5Ah pouch batteries C1, C2, C3 and pouch battery D, respectively. And carrying out electrochemical performance tests such as direct current internal resistance, circulation performance, liquid absorption speed and the like, and safety tests such as puncture experiments, impact experiments and the like.
And (3) electrochemical performance testing: taking the lithium ion batteries prepared in the embodiments 2-4 and the comparative example, the test method comprises the following steps: the preparation of the coated graphite composite material refers to freedomCAR battery test manual, and a cycle performance test method (charge-discharge multiplying power is 1.0C/1.0C, and voltage range is 2.5-3.65V); the method for testing the imbibition speed comprises the following steps: in the glove box, a negative pole piece of 1cm × 1cm is selected, electrolyte is sucked in a burette and titrated on the pole piece until the electrolyte is obviously absent on the surface of the pole piece, and time and the dropping amount of the electrolyte are recorded. The test results are shown in table 2 below.
TABLE 2 comparison of lithium ion Battery Performance prepared in examples and comparative examples
As can be seen from table 2, the batteries of the examples are superior to the comparative examples in terms of direct current internal resistance, cycle performance and liquid absorption rate, because the protective layer on the surface of the negative electrode material in the examples contains aminated graphene, and reacts with SO2 to generate thiolated graphene, forming a network structure to improve the structural stability of the material, and meanwhile, the electronic conductivity of the material is improved by virtue of the high specific surface area and conductivity of graphene, SO that the internal resistance of the battery is reduced and the cycle performance of the lithium ion battery is improved.
Puncture test: 10 batteries of each of examples 2 to 4 and comparative example were taken, and after the batteries were fully charged, a nail having a diameter of 2.0mm to 25mm was inserted through the center of the battery, a temperature tester was installed at the terminal of the battery, the nail was left in the battery, the condition of the battery was observed, and the temperature of the battery was measured. See table 3 below.
TABLE 3 puncture test comparison of examples and comparative examples
As can be seen from table 3, in examples 2 to 4, the surface is coated with the thermal denaturation material to increase the safety coefficient thereof, which is caused by that the local temperature of the battery is too high when the battery is abnormally used, such as short circuit, and the thermal denaturation material has high heat dissipation performance and self-closing function, so that the safety performance of the battery can be improved.
Impact test: after 10 batteries of examples 2 to 4 and comparative example were each charged, a 16.0mm diameter rigid rod was laid across the batteries, dropped from a height of 610mm with a 20 pound weight, and crushed on the rigid rod to observe the condition of the batteries.
TABLE 3 comparison of impact tests of examples and comparative examples
As can be seen from Table 3, the lithium ion battery prepared in the example is obviously due to the comparative example in the aspect of impact test, and the reason is that the battery in the example adopts the thermal denaturation material, and when the temperature of the battery is too high, the surface of the material is self-closed, so that the safety performance of the battery is improved.
Secondly, according to the method of the embodiment, the thermal denaturation material adopts ethylene-vinyl acetate copolymer, polymethyl methacrylate, polystyrene or polyacrylate, and the binder adopts polyvinyl alcohol, sodium carboxymethyl cellulose, styrene butadiene rubber, polyacrylate, polyacrylonitrile or polyacrylamide, which can realize the functions and have the indexes which are not different from those of the examples 2-4. .
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The high-safety lithium ion battery cathode composite material is characterized in that: the core is graphite, and the coating layer is made of thermal denaturation composite materials and is 0.5-1 mu m thick.
2. The high-safety lithium ion battery negative electrode composite material as claimed in claim 1, wherein the thermal denaturation composite material comprises the following components in parts by weight: 50-60 parts of thermal denaturation material, 1-5 parts of aminated graphene, 0.5-2 parts of functional additive and 40-50 parts of binder.
3. The high-safety lithium ion battery negative electrode composite material as claimed in claim 2, wherein the thermal denaturation material is one or more of ethylene-vinyl acetate copolymer, polymethyl methacrylate, polystyrene and polyacrylate.
4. The high-safety lithium ion battery negative electrode composite material of claim 2, wherein the amino group content in the aminated graphene is 0.1% -5%.
5. The high-safety lithium ion battery negative electrode composite material of claim 2, wherein the functional additive comprises the following components in parts by weight: 60-80 parts of ammonium benzene sulfonate and 20-40 parts of ethylene glycol monobutyl ether.
6. The high-safety lithium ion battery negative electrode composite material as claimed in claim 2, wherein the binder is one or more of polyvinyl alcohol, sodium carboxymethylcellulose, styrene-butadiene rubber, polyacrylate, polyacrylonitrile and polyacrylamide.
7. A preparation method of a high-safety lithium ion battery cathode composite material is characterized in that the lithium ion battery cathode is the composite material of any one of claims 1 to 6, and the preparation method comprises the following steps:
A. preparing a heat-denatured composite material coating liquid;
B. weighing 100-200 parts of graphite with the particle size of 5-10 mu m, adding the graphite into a coating liquid, uniformly dispersing the graphite in a ball mill, drying, crushing and grading to obtain a graphite composite material, transferring the graphite composite material into a tube furnace, introducing inert gas to discharge gas in the tube, and introducing SO2Heating the gas to 100-300 ℃, keeping the pressure in the pipe at 1-1.2 Mpa, and keeping the temperature for 1-6 h; stopping the introduction of SO2Introducing inert gas into the gas, and naturally cooling to room temperature to obtain the coated graphite composite material.
8. The preparation method of the high-performance lithium ion battery cathode according to claim 7, wherein the specific method in the step A is as follows:
adding 40-50 parts of binder into 100 parts of N-methyl pyrrolidone organic solvent, uniformly stirring, adding 50-60 parts of thermal denaturation material, uniformly dissolving, adding 1-5 parts of aminated graphene and 0.5-2 parts of functional additive, and uniformly dispersing by ultrasonic to obtain uniform coating liquid.
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| CN116759574A (en) * | 2023-08-16 | 2023-09-15 | 深圳海辰储能控制技术有限公司 | Negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium battery |
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