CN107644990B - Metallic lithium negative electrode material with positive temperature coefficient effect - Google Patents
Metallic lithium negative electrode material with positive temperature coefficient effect Download PDFInfo
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- CN107644990B CN107644990B CN201610577909.2A CN201610577909A CN107644990B CN 107644990 B CN107644990 B CN 107644990B CN 201610577909 A CN201610577909 A CN 201610577909A CN 107644990 B CN107644990 B CN 107644990B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a metallic lithium cathode material with positive temperature coefficient effect, which is prepared by the following steps: (1) cutting lithium metal into slices under the protection of argon, mixing the slices with hydrocarbon oil containing 0.1-0.3% of coupling agent, and heating and melting the lithium metal under the stirring condition to obtain molten liquid; (2) cooling the molten liquid to 70-80 ℃, adding the coating liquid, stirring and simultaneously applying a pulse magnetic field, and maintaining for 20-30min to obtain a dispersion system; (3) filtering the dispersion system under the protection of argon, washing the filtered substance with an organic solvent to remove a hydrocarbon oil medium, and drying in vacuum at 70-80 ℃ to obtain a finished product. The invention can be stored for a long time, is not influenced by environment, has good stability, does not reduce the conductive performance and has positive temperature coefficient effect, when the temperature is raised to the transition temperature of the cladding material, the impedance of the cladding material is sharply increased, the transmission of electrons and ions can be cut off, and the overtemperature protection effect is realized.
Description
Technical Field
The invention relates to a lithium battery cathode material, in particular to a metallic lithium cathode material with positive temperature coefficient effect.
Background
Lithium metal plays a very important role in modern industry and science and technology, and is widely applied to the fields of electronics, chemical industry, medicine, glass, rubber, ceramics, nuclear industry, aerospace, metal smelting, mechanical manufacturing and the like. The metal lithium battery directly utilizes the metal lithium, the energy reserve amount of the metal lithium battery is more than twice of that of the traditional lithium ion battery, and in the aspect of discharge capacity, even reaches about 10 times of that of the traditional product, and the metal lithium battery is expected to replace the lithium ion battery. Lithium is widely used as a main material of a cathode in the development of high-energy batteries and secondary batteries for rechargeable battery panels of mobile phones, and the annual demand of only this japan is around 7 billion. The negative electrode materials of the power supply for the emission of the two missiles, such as the LI-SI alloy, the LI-AL alloy and the like, help the novel missiles in China fly to the blue sky.
Lithium metal has high activity, is easily self-ignited in air, and is very reactive with water, and the properties limit the application of the lithium metal in many aspects. Therefore, in order to use lithium in a normal environment, it is necessary to obtain stabilized lithium metal by a certain means.
By drying CO as described in U.S. Pat. Nos. 5,567,474, 5,776,369, and 5,976,4032Treating the metallic lithium to obtain a layer of Li on the surface2CO3And (5) passivating the film. The CO2 passivated lithium metal powder can only be used in low humidity environments and is not stored for long periods of time. Chinese patent No. CN 103447541 a proposes a method of treating molten lithium metal with a phosphorus-containing compound to obtain a continuous protective layer of lithium phosphate. Another option is to coat the lithium powder with a protective layer. For example, U.S. patent No. 6,911,280B1 proposes coating with an alkali metal or alkaline earth metal carbonate. U.S. Pat. No. 4,503,088 proposes coating an epoxy resin on a lithium negative electrode as a passivation layer. The outer layer cladding of the prior art is an inorganic compound or an organic matter, the cladding is non-conductive, the conductivity of the metal lithium is reduced, the cladding is conductive, but the cladding does not have an overtemperature protection effect, and the safety performance is poor.
Disclosure of Invention
The invention aims to provide a metallic lithium cathode material with positive temperature coefficient effect, which can be stored for a long time, is not influenced by environment, has good stability, has no reduction of conductive performance, has positive temperature coefficient effect, and can cut off electron and ion transmission and play a role in overtemperature protection when the impedance of a cladding material is sharply increased when the temperature is increased to the transition temperature of the cladding material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a metallic lithium negative electrode material with positive temperature coefficient effect is prepared by the following steps:
(1) cutting lithium metal into slices under the protection of argon, mixing the slices with hydrocarbon oil containing 0.1-0.3% of coupling agent, heating and melting the lithium metal under the stirring condition to obtain molten liquid, wherein the mass ratio of the lithium metal: the weight ratio of hydrocarbon oil is 1:1.5-1: 2;
(2) cooling the molten liquid to 70-80 ℃, adding the coating liquid, stirring and simultaneously applying a pulse magnetic field, and maintaining for 20-30min to obtain a dispersion system;
(3) filtering the dispersion system under the protection of argon, washing the filtered substance with an organic solvent to remove a hydrocarbon oil medium, and drying in vacuum at 70-80 ℃ to obtain a finished product.
The lithium metal cathode material prepared by the specific process has the advantages of uniform surface coating of the lithium metal, good coating effect, long-term storage, no environmental influence, good stability, unreduced conductivity and positive temperature coefficient effect, and when the temperature rises to the transition temperature of the coating material, the impedance of the coating material is increased sharply, so that the transmission of electrons and ions can be cut off, and the overtemperature protection effect is realized. The melting liquid of the invention must be cooled to 70-80 ℃ before the cladding liquid can be added, if the temperature of the melting liquid is too high, the positive temperature coefficient effect of the cladding can be triggered, and the product is invalid. The invention firstly uses hydrocarbon oil containing 0.1-0.3% of coupling agent to melt metal lithium, and has melting and surface treatment effects, so that a coating can be better combined with lithium.
Preferably, the coupling agent in step (1) is a silane coupling agent.
Preferably, the temperature for heating and melting the metallic lithium in the step (1) is controlled to 200. + -. 10 ℃.
Preferably, in the step (2), the coating liquid is formed by mixing a coating with positive temperature coefficient effect and hydrocarbon oil, the mass concentration of the coating with positive temperature coefficient effect is 20-30%, and the coating with positive temperature coefficient effect: the mass ratio of the metal lithium =1: 20-25.
Preferably, the coating with positive temperature coefficient effect is one or more of poly 3-methylthiophene (P3 MT), poly 3-decylthiophene (P3 DT) and poly 3-butylthiophene (P3 BT). The invention selects the specific coating, so that the product can be stored for a long time, is not influenced by the environment, has good stability, can conduct electricity by the coating, does not reduce the conductivity of the coated lithium metal, has a special positive temperature coefficient effect, and has the advantages that when the temperature is increased to the transition temperature (110-160 ℃) of the coating material, the impedance of the coating material is increased sharply, the transmission of electrons and ions can be cut off, and the overtemperature protection effect is realized.
Preferably, the stirring in step (2) is performed while applying a pulse electric field, the stirring speed is 800-1200rmp, the pulse voltage of the pulse magnetic field is 100-120V, and the pulse frequency is 20-25 Hz.
Preferably, the organic solvent washing in step (3) is three times hexane washing and one time n-pentane washing.
Preferably, the hydrocarbon oil is one of mineral oil, petroleum oil, shale oil and paraffin oil.
The invention has the beneficial effects that: the coating material can be stored for a long time, is not influenced by the environment, has good stability, does not reduce the conductivity, has positive temperature coefficient effect, and has the advantages that when the temperature is increased to the transition temperature of the coating material, the impedance of the coating material is increased sharply, the transmission of electrons and ions can be cut off, and the overtemperature protection effect is realized.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a metallic lithium negative electrode material with positive temperature coefficient effect is prepared by the following steps:
(1) cutting 1kg of lithium metal (battery grade lithium metal) into 3 × 3cm pieces under the protection of argon, mixing with 1.5kg of hydrocarbon oil (mineral oil, commercially available) containing 0.3wt% of silane coupling agent KH560, and heating to about 200 deg.C under stirring to melt the lithium metal to obtain a melt;
(2) cooling the molten liquid to 70 ℃, adding a hydrocarbon oil (mineral oil, commercially available) solution of poly-3-methylthiophene with a mass concentration of 20%, poly-3-methylthiophene: simultaneously applying a pulse magnetic field under the stirring condition of the mass ratio of the metal lithium =1: 25 and 800rmp, wherein the pulse voltage of the pulse magnetic field is 120V at 100-25 Hz, and the pulse frequency is 20-25 Hz, and maintaining for 30min to obtain a dispersion system;
(3) filtering the dispersion system under the protection of argon, washing the filtered substance with hexane for three times, washing the filtered substance with n-pentane for one time to remove a hydrocarbon oil medium, and drying the product in vacuum at 70 ℃ to obtain a finished product.
Example 2:
a metallic lithium negative electrode material with positive temperature coefficient effect is prepared by the following steps:
(1) cutting 1kg of lithium metal (battery grade lithium metal) into 3 × 3cm pieces under the protection of argon, mixing with 2kg of hydrocarbon oil (paraffin oil, commercially available) containing 0.1wt% of silane coupling agent KH570, and heating to about 200 deg.C under stirring to melt the lithium metal to obtain molten solution;
(2) cooling the melt to 80 ℃, adding a hydrocarbon oil (paraffin oil, commercially available) solution of poly-3-decylthiophene with a mass concentration of 30%, poly-3-decylthiophene: simultaneously applying a pulse magnetic field under the stirring condition of the mass ratio of the metal lithium =1:20 and 1200rmp, wherein the pulse voltage of the pulse magnetic field is 120V at 100-25 Hz, and the pulse frequency is maintained for 20min to obtain a dispersion system;
(3) filtering the dispersion system under the protection of argon, washing the filtered substance with hexane for three times, washing the filtered substance with n-pentane for one time to remove a hydrocarbon oil medium, and drying the product in vacuum at the temperature of 80 ℃ to obtain a finished product.
Example 3:
a metallic lithium negative electrode material with positive temperature coefficient effect is prepared by the following steps:
(1) cutting 1kg of lithium metal (battery grade lithium metal) into 3 × 3cm pieces under argon protection, mixing with 2kg of hydrocarbon oil (mineral oil, commercially available) containing 0.2% of silane coupling agent KH560, and heating to about 200 deg.C under stirring to melt the lithium metal to obtain a molten solution;
(2) cooling the molten liquid to 75 ℃, adding a hydrocarbon oil (mineral oil, commercially available) solution of poly-3-butylthiophene with a mass concentration of 25%, wherein the mass concentration of poly-3-butylthiophene: simultaneously applying a pulse magnetic field under the stirring condition of the mass ratio of the metal lithium =1: 25 and 1000rmp, wherein the pulse voltage of the pulse magnetic field is 120V at 100-;
(3) filtering the dispersion system under the protection of argon, washing the filtered substance with hexane for three times, washing the filtered substance with n-pentane for one time to remove a hydrocarbon oil medium, and drying the product in vacuum at 75 ℃ to obtain a finished product.
Preparing a negative plate: mixing the prepared metal lithium negative electrode material with a binder PVDF according to a weight ratio of 95:5, dissolving in an organic solvent NMP, coating on a current collector copper foil, and rolling and slitting a pole piece to prepare a negative pole piece.
Preparing a positive plate: selecting a lithium-rich manganese-based material as a positive electrode material, mixing positive electrode slurry according to the weight ratio of 90: 5 of a positive electrode active material, a conductive agent and a binder, and uniformly coating the positive electrode slurry on a positive electrode-based fluid aluminum foil. After drying, rolling by a rolling machine, and then slitting to prepare the positive pole piece.
Preparing a diaphragm: a commercial PE separator was selected.
Preparing electrolyte: an electrolyte solution of commercial LiPF6 dissolved in an organic solution was selected.
Preparing a battery: and preparing a battery core by laminating the positive and negative pole pieces and the diaphragm, packaging the battery core in an aluminum plastic film, injecting electrolyte, sealing and forming to obtain the lithium metal negative electrode battery.
The energy density of the battery can reach 500-550Wh/kg, and the battery has very good safety performance through safety tests such as overcharge, overdischarge, needling, extrusion and the like.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (5)
1. The metallic lithium negative electrode material with the positive temperature coefficient effect is characterized by being prepared by the following steps:
(1) cutting lithium metal into slices under the protection of argon, mixing the slices with hydrocarbon oil containing 0.1-0.3% of silane coupling agent, heating and melting the lithium metal under the stirring condition to obtain molten liquid, wherein the mass ratio of the lithium metal: the weight ratio of hydrocarbon oil is 1:1.5-1: 2;
(2) cooling the molten liquid to 70-80 ℃, adding the coating liquid, stirring and simultaneously applying a pulse magnetic field, and maintaining for 20-30min to obtain a dispersion system; the coating liquid is formed by mixing a coating with a positive temperature coefficient effect with hydrocarbon oil, wherein the coating is one or more of poly-3-methylthiophene, poly-3-decylthiophene and poly-3-butylthiophene;
(3) filtering the dispersion system under the protection of argon, washing the filtered substance with an organic solvent to remove a hydrocarbon oil medium, washing the filtered substance with the organic solvent for three times, washing the filtered substance with hexane for one time, and drying the washed substance in vacuum at 70-80 ℃ to obtain a finished product.
2. The lithium metal anode material with positive temperature coefficient effect according to claim 1, wherein: the temperature for heating and melting the metallic lithium in the step (1) is controlled to be 200 +/-10 ℃.
3. The lithium metal anode material with positive temperature coefficient effect according to claim 1 or 2, characterized in that: the mass concentration of the cladding with the positive temperature coefficient effect in the step (2) is 20-30%, and the cladding with the positive temperature coefficient effect: the mass ratio of the metal lithium =1: 20-25.
4. The lithium metal anode material with positive temperature coefficient effect according to claim 1 or 2, characterized in that: and (3) applying a pulse electric field while stirring in the step (2), wherein the stirring speed is 800-.
5. The lithium metal anode material with positive temperature coefficient effect according to claim 1 or 2, characterized in that: the hydrocarbon oil is one of mineral oil, petroleum, shale oil and paraffin oil.
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| CN112993251B (en) * | 2019-12-16 | 2023-12-12 | 比亚迪股份有限公司 | Lithium supplementing material, preparation method thereof, negative electrode and lithium ion battery |
| CN111816836B (en) * | 2020-07-20 | 2021-09-17 | 四川虹微技术有限公司 | Composite lithium metal negative electrode material and preparation method thereof |
| CN112267026B (en) * | 2020-10-13 | 2023-01-31 | 湖南金凯循环科技有限公司 | Method for preparing lithium hydroxide by taking waste lithium metal as raw material |
| CN114798503B (en) * | 2022-06-07 | 2023-12-08 | 蜂巢能源科技股份有限公司 | Safety-based lithium ion battery screening method and device and electronic equipment |
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