WO2021120927A1 - 一种补锂材料及其制备方法、负极和锂离子电池 - Google Patents
一种补锂材料及其制备方法、负极和锂离子电池 Download PDFInfo
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- WO2021120927A1 WO2021120927A1 PCT/CN2020/128047 CN2020128047W WO2021120927A1 WO 2021120927 A1 WO2021120927 A1 WO 2021120927A1 CN 2020128047 W CN2020128047 W CN 2020128047W WO 2021120927 A1 WO2021120927 A1 WO 2021120927A1
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- lithium
- particles
- dispersion liquid
- carbon nanotubes
- conductive material
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 328
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 239000000463 material Substances 0.000 title claims abstract description 95
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 139
- 239000004020 conductor Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims description 99
- 239000013589 supplement Substances 0.000 claims description 88
- 239000007788 liquid Substances 0.000 claims description 72
- 239000002048 multi walled nanotube Substances 0.000 claims description 63
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 41
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- 239000002041 carbon nanotube Substances 0.000 claims description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 33
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 19
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- 239000004094 surface-active agent Substances 0.000 claims description 11
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
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- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 16
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to the field of lithium ion batteries, and in particular, to a lithium supplement material and a preparation method thereof, a negative electrode, and a lithium ion battery.
- Lithium-ion batteries have the advantages of high specific energy and long cycle life, and have been widely used in various portable electronic devices such as notebook computers and mobile phones. With the increasing severity of energy and environmental issues, countries are increasingly demanding energy conservation and emission reduction. Traditional fuel vehicles not only consume oil, which has limited reserves of fossil energy, but also have serious exhaust pollution. Therefore, electric vehicles came into being. As the main energy storage unit of electric vehicles, lithium-ion power batteries have received more and more attention and have shown good development prospects. With the continuous improvement of people's requirements for cruising range and driving experience, it is particularly important to increase the energy density of power batteries, which can be achieved by optimizing the battery structure, using higher capacity electrode materials, and expanding the operating voltage of the battery.
- the organic electrolyte is reduced and decomposed on the surface of the negative electrode such as graphite to form a solid electrolyte phase interface (SEI) film, which permanently consumes the lithium ions extracted from the positive electrode, causing irreversible capacity loss and reducing the initial charge.
- SEI solid electrolyte phase interface
- the theoretical specific capacity of traditional graphite anode material is 372mAh/g, and the first irreversible capacity loss is 5%-10%.
- high-capacity anode materials, such as silicon and alloys the first irreversible capacity is higher.
- prelithiation technology is used to offset the lithium ions consumed when the material is formed when the SEI film is formed to increase the total capacity of the battery.
- the current prelithiation technology can be roughly divided into negative electrode lithium supplement, positive electrode lithium supplement, separator lithium supplement, and electrolyte lithium supplement.
- Common negative electrode lithium supplements include lithium foil supplementation and lithium powder supplementation.
- the potential of metallic lithium is the lowest among all electrode materials. Due to the existence of the potential difference, when the negative electrode material contacts the metallic lithium foil or lithium powder, electrons will spontaneously move to the negative electrode, allowing lithium ions to be inserted into the negative electrode.
- the lithium supplementation material is pressed or coated on the surface of the negative electrode material, when the lithium metal and graphite are not in contact or the lithium supplementation layer closest to the negative electrode material is consumed, dead lithium is easily formed, which greatly reduces the efficiency of lithium supplementation, and may also form branches. Crystal, causing safety hazards.
- the purpose of the present disclosure is to provide a lithium supplement material which has high lithium supplement efficiency and avoids the formation of dead lithium to cause dendrites.
- the present disclosure provides a lithium supplement material
- the lithium supplement material includes metallic lithium particles and a conductive material
- the conductive material includes a built-in section embedded in the metallic lithium particles and located outside the metallic lithium particles The exposed section; the electronic conductivity of the conductive material is greater than 100s/cm.
- the conductive material is a carbon material; the carbon material is selected from at least one of carbon nanotubes, carbon fibers, and graphene;
- the carbon material is carbon nanotubes; the carbon nanotubes are single-walled carbon nanotubes and/or multi-walled carbon nanotubes, preferably multi-walled carbon nanotubes; and/or, the carbon nanotubes are
- the tube diameter is 5nm-100nm, preferably 10nm-30nm, and the length is 10 ⁇ m-80 ⁇ m, preferably 30 ⁇ m-50 ⁇ m.
- the content of the conductive material is 0.1-3 parts by weight, preferably 0.5-1 parts by weight.
- the average particle size of the metallic lithium particles is 20 ⁇ m-40 ⁇ m; and/or,
- the surface of the metal lithium particles has a passivation layer; the thickness of the passivation layer is 5 nm-100 nm; the passivation layer contains at least one of lithium carbonate, lithium fluoride, and paraffin wax.
- a second aspect of the present disclosure provides a method for preparing a lithium supplement material, the method comprising:
- the conductive material is a carbon material; the carbon material is selected from at least one of carbon nanotubes, carbon fibers, and graphene; preferably, the carbon material is single-walled carbon nanotubes and / Or multi-walled carbon nanotubes, preferably multi-walled carbon nanotubes; the diameter of the carbon nanotubes is 5nm-100nm, preferably 10nm-30nm, the length is 10 ⁇ m-80 ⁇ m, preferably 30 ⁇ m-50 ⁇ m; and/or ,
- the first dispersion liquid also contains a surfactant;
- the surfactant is selected from at least one of polyvinylpyrrolidone, sodium dodecylbenzene sulfonate and cetyltrimethylamine bromide, preferably Polyvinylpyrrolidone; the weight ratio of the metal lithium and the surfactant is 1: (0.002-0.05), preferably 1: (0.005-0.02); and/or,
- the dispersion medium of the first dispersion liquid and the second dispersion liquid is an inert organic solvent, and the dispersion medium of the first dispersion liquid and the second dispersion liquid are each independently selected from the group consisting of hydrocarbons, esters, ethers, and silicone oils. At least one; and/or,
- the volume ratio of the first dispersion to the second dispersion is 1: (0.1-10), preferably 1: (0.5-3); the weight ratio of the metallic lithium to the conductive material is 100: (0.1-3), preferably 100: (0.5-1).
- the method further includes: in step S1, carbon dioxide is introduced after the first dispersion liquid and the second dispersion liquid are uniformly mixed.
- the third aspect of the present disclosure provides a lithium supplement material prepared by the method provided in the second aspect of the present disclosure.
- a fourth aspect of the present disclosure provides a lithium ion battery negative electrode, which includes a current collector, a negative electrode active material, and a lithium supplement material.
- the lithium supplement material is described in any one of the first aspect of the present disclosure and the third aspect of the present disclosure. Lithium supplement material.
- a fifth aspect of the present disclosure provides a lithium ion battery, which includes the lithium ion battery negative electrode provided in the fourth aspect of the present disclosure.
- the lithium supplement material of the present disclosure can realize the electronic conduction between the lithium metal particles and the negative electrode active material through the conductive material, increase the electronic conduction channel, and at the same time facilitate the transmission of lithium ions, and realize the rapid insertion process of lithium ions.
- the efficiency of replenishing lithium is significantly improved, thereby effectively inhibiting the formation of dead lithium and avoiding the formation of dendrites piercing the diaphragm and causing safety hazards.
- FIG. 1 is a schematic diagram of the principle of lithium supplementation when the lithium supplement material of the present disclosure is applied to the negative electrode of a lithium ion battery.
- a first aspect of the present disclosure provides a lithium supplement material.
- the lithium supplement material includes metallic lithium particles and a conductive material.
- the conductive material includes a built-in section embedded in the metallic lithium particles and an exposed portion outside the metallic lithium particles. Section;
- the electronic conductivity of the conductive material is greater than 100s/cm.
- the conductive material may be a one-dimensional material and/or a two-dimensional material with an electronic conductivity greater than 100 s/cm.
- the conductive material includes a built-in section buried in the metal lithium particles and an exposed section located outside the metal lithium particles.
- the conductive material may be inserted into the metal lithium particles.
- the conductive material has a longer length. When it is larger than the particle size of the metal lithium particles, the conductive material may penetrate one or even several of the metal lithium particles.
- the conductive material includes a plurality of built-in segments embedded in the metal lithium particles and a plurality of exposed segments located outside the metal lithium particles, and the conductive material can be bent; in another embodiment, The length of the conductive material is relatively short.
- the conductive material may only partially embed the lithium metal particles.
- the conductive material only includes one embedded in the lithium metal particles.
- the inventors of the present disclosure have discovered that when a portion of the conductive material in the lithium supplement material is embedded with metal lithium particles, the lithium supplement material is rolled with the negative electrode sheet without lithium supplement, and the conductive material can be tightly connected with the negative electrode active material.
- Forming a vertical three-dimensional conductive network not only can realize the electronic conduction between the lithium metal particles and the solid-phase interface of the negative electrode material, but also can realize the electronic conduction between the metal lithium particles and the negative electrode active material through the conductive material, increasing the electron conduction channel, and at the same time It helps the transmission of lithium ions, realizes the rapid insertion process of lithium ions, and significantly improves the efficiency of lithium supplementation, thereby effectively inhibiting the formation of dead lithium, and avoiding the formation of dendrites that pierce the diaphragm and cause safety hazards.
- the conductive material may be a carbon material known in the art.
- the carbon material may be selected from at least one of carbon nanotubes, carbon fibers, and graphene.
- the carbon material may be carbon nanotubes.
- the carbon nanotubes have a one-dimensional tubular structure through which electrons can conduct high-speed conduction and therefore have excellent electronic conductivity.
- the metal lithium particles are relatively large in size and have a diameter of several tens of micrometers. , The bending and winding shape of carbon nanotubes is more conducive to interspersing to form a conductive network.
- the carbon nanotubes are known in the art.
- the carbon nanotubes are at least one of single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
- the carbon nanotubes may be multi-walled carbon nanotubes.
- the diameter of the carbon nanotubes may be 5nm-100nm, preferably 10nm-30nm, and the length may be 10 ⁇ m-80 ⁇ m, preferably 30 ⁇ m-50 ⁇ m.
- the content of the conductive material can be changed within a certain range.
- a conductive network of an appropriate proportion is provided.
- the content may be 0.1-3 parts by weight.
- the content of the conductive material may be 0.5-1 parts by weight.
- the average particle size of the metal lithium particles can be varied within a relatively large range, and preferably, the average particle size can be 20 ⁇ m-40 ⁇ m.
- the average particle size of the metal lithium particles can be observed by scanning electron microscope to measure the particle size of any 100 metal lithium particles randomly, and the average particle size is the average particle size of the metal lithium particles.
- the metallic lithium particles in order to effectively prevent the internal metallic lithium from further reacting in contact with oxygen, carbon dioxide and moisture in the air, the metallic lithium particles also have a passivation layer on the surface; the passivation layer may be chemically stable At least one of the lithium carbonate layer, the lithium fluoride layer and the paraffin wax layer, the thickness of the passivation layer can vary in a relatively large range, for example, the thickness of the passivation layer can be 5-100nm, preferably In an embodiment, the thickness of the passivation layer may be 10-30 nm.
- a second aspect of the present disclosure provides a method for replenishing lithium materials, which specifically includes:
- the conductive material may be a carbon material known in the art.
- the carbon material may be selected from at least one of carbon nanotubes, carbon fibers, and graphene.
- the carbon material may be carbon nanotubes.
- the carbon nanotubes have a one-dimensional tubular structure through which electrons can conduct high-speed conduction. Therefore, they have excellent electronic conductivity.
- the metal lithium particles have a relatively large volume and a diameter of several The ten micron level, therefore, the bending and winding shape of carbon nanotubes is more conducive to interspersing to form a conductive network.
- the carbon nanotubes are known in the art.
- the carbon nanotubes may be at least one of single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
- the carbon nanotubes may be multi-walled carbon nanotubes.
- the diameter of the carbon nanotubes may be 5nm-100nm, preferably 10nm-30nm, and the length may be 10 ⁇ m-80 ⁇ m, preferably 30 ⁇ m-50 ⁇ m.
- the first dispersion liquid may also contain a surfactant, which is known in the art, for example, the surfactant may be selected from polyvinylpyrrolidone, dodecyl One or more of sodium benzene sulfonate and cetyltrimethyl amine bromide.
- the surfactant may be polyvinylpyrrolidone.
- the weight ratio of the metal lithium and the surfactant can be changed within a certain range. For example, the weight ratio of the metal lithium and the surfactant can be 1:(0.002-0.05), preferably 1:( 0.005-0.02).
- the dispersion medium of the first dispersion liquid and the second dispersion liquid are inert organic solvents commonly used in the art, and the dispersion medium of the first dispersion liquid and the second dispersion liquid can be independently selected from each other.
- At least one of hydrocarbons, esters, ethers, and silicone oils can be selected from at least one of hydrocarbon oils, white oils and silicone oils commonly used in the art.
- the dispersion medium of the first dispersion liquid and the second dispersion liquid may be silicone oil, such as common methyl silicone oil, ethyl silicone oil, and methyl ethoxy silicone oil. Go into details.
- the volume ratio of the first dispersion liquid and the second dispersion liquid may be varied within a relatively large range, for example, the volume ratio of the first dispersion liquid and the second dispersion liquid may be 1: (0.1-10), preferably 1: (0.5-3).
- the weight ratio of the metal lithium to the conductive material can be varied within a relatively large range.
- the weight ratio of the metal lithium to the conductive material can be 100: (0.1-3), preferably 100: (0.5). -1).
- the method may further include the step of introducing carbon dioxide to form a passivation layer.
- a passivation layer For example, in step S1, after the first dispersion liquid and the second dispersion liquid are mixed, an inert gas containing carbon dioxide is introduced.
- the gas may be high-purity carbon dioxide.
- the third aspect of the present disclosure provides a lithium supplement material prepared by the method provided in the second aspect of the present disclosure.
- a fourth aspect of the present disclosure provides a lithium ion battery negative electrode, which includes a current collector, a negative active material, and a lithium supplement material.
- the lithium supplement material is the supplement provided in the first aspect of the present disclosure and/or the third aspect of the present disclosure. Lithium material.
- the anode current collector may be a conventional anode current collector in a lithium ion battery, such as stamped metal, metal foil, mesh metal, and foam metal.
- the negative active material may also include a binder, the type of which may be conventional in the art, and will not be repeated here.
- the method for preparing the negative electrode of the lithium ion battery of the present disclosure has no special requirements and can be carried out with reference to the prior art.
- the method for preparing the negative electrode of the lithium ion battery of the present disclosure may include: coating a negative electrode slurry containing a negative electrode active material and a binder. Coated and/or filled on the negative electrode current collector, and then dried and rolled.
- the specific operation methods and conditions can be conventional in the field, and there are no special restrictions here.
- Figure 1 is a schematic diagram of the principle of lithium supplementation when the lithium supplement material of the present disclosure is applied to the negative electrode of a lithium ion battery.
- the conductive material 2 such as carbon nanotubes
- the conductive material 2 can be wound through the metal Lithium particles 1, after rolling, the bent and wound conductive material 2 can be closely connected with the negative electrode active material 3 to form a vertical three-dimensional conductive network, which can not only realize the particle conduction of the solid phase interface between the metal lithium particles 1 and the negative electrode active material 3
- the metal lithium particles 1 that are not in contact with the negative electrode active material 3 can also transfer the particles to the negative electrode active material 3 through the conductive material 2, and the metal lithium particles 1 can realize the electronic conduction process with the negative electrode active material 3 through the conductive material 2. It helps the transmission of lithium ions and realizes the rapid insertion process of lithium ions, thereby effectively inhibiting the formation of dead lithium, significantly improving the efficiency of replenishing lithium, and avoiding the formation of dendrites which may cause
- a fifth aspect of the present disclosure provides a lithium ion battery, which includes the lithium ion battery negative electrode provided in the fourth aspect of the present disclosure.
- a lithium ion battery may also include a positive electrode, a separator, and an electrolyte.
- the present disclosure has no special restrictions on the positive electrode, separator, and electrolyte, and may be conventional types in the field.
- the lithium ion battery may also use conventional methods in the field.
- the positive electrode and the negative electrode of the present disclosure are wound and separated by a separator to form an electrode group, and the obtained electrode group and electrolyte are sealed in a battery case to obtain the lithium ion battery provided by the present disclosure.
- the winding method of the separator between the positive electrode and the negative electrode is well known to those skilled in the art, and will not be repeated here.
- Multi-walled carbon nanotubes purchased from Jiangsu Tiannai Technology Co., Ltd., have an electronic conductivity of >150s/cm.
- Single-walled carbon nanotubes purchased from Jiangsu Tiannai Technology Co., Ltd., have an electronic conductivity> 150s/cm.
- Carbon fiber purchased from Jiangsu Tiannai Technology Co., Ltd., has an electronic conductivity of >100s/cm.
- Graphene purchased from Jiangsu Tiannai Technology Co., Ltd., has an electronic conductivity> 100s/cm.
- a dispersion liquid take 0.05g of multi-walled carbon nanotubes with a diameter of 10nm and a length of 50 ⁇ m, add 25g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion;
- the second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain the lithium supplement material A1.
- the lithium supplement material A1 of Example 1 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes are partially embedded in the metallic lithium particles, and the multi-walled carbon nanotubes can be It includes a built-in section buried in the lithium metal particles and an exposed section located outside the lithium metal particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 27.8 ⁇ m, and the thickness of the lithium carbonate layer was 21 nm.
- the ingot is completely dissolved to obtain the first dispersion; take 0.05 g of multi-walled carbon nanotubes with a diameter of 10 nm and a length of 50 ⁇ m, add 25 g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion; Under stirring conditions, the second dispersion is slowly added to the first dispersion and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A2.
- the lithium supplement material A2 of Example 2 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. The test found that the average particle size of the lithium metal particles was 42.2 ⁇ m, and the thickness of the lithium carbonate layer was 27 nm.
- the lithium supplement material A3 of Example 3 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 45.4 ⁇ m, and the thickness of the lithium carbonate layer was 35 nm.
- a dispersion liquid take 0.05g of multi-walled carbon nanotubes with a diameter of 20nm and a length of 30 ⁇ m, add 25g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion;
- the second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A4.
- the lithium supplement material A4 of Example 4 includes metallic lithium particles, multi-walled carbon nanotubes and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 26.2 ⁇ m, and the thickness of the lithium carbonate layer was 27 nm.
- a dispersion liquid Take 0.05g of multi-walled carbon nanotubes with a diameter of 40nm and a length of 20 ⁇ m, add 25g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion; The second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A5.
- the lithium supplement material A5 of Example 5 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 29.2 ⁇ m, and the thickness of the lithium carbonate layer was 20 nm.
- a dispersion liquid take 0.05g of multi-walled carbon nanotubes with a tube diameter of 60nm and a length of 20 ⁇ m, add 25g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion;
- the second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A6.
- the lithium supplement material A6 of Example 6 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically, a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metallic lithium particles was 39.6 ⁇ m, and the thickness of the lithium carbonate layer was 23 nm.
- a dispersion liquid Take 0.08g of multi-walled carbon nanotubes with a diameter of 20nm and a length of 30 ⁇ m, add 25g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion; The second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A7.
- the lithium supplement material A7 of Example 7 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. The test found that the average particle size of the metal lithium particles was 25.0 ⁇ m, and the thickness of the lithium carbonate layer was 22 nm.
- a dispersion liquid take 0.1 g of multi-walled carbon nanotubes with a diameter of 20 nm and a length of 30 ⁇ m, add 25 g of silicone oil, and stir at 200 °C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion;
- the second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A8.
- the lithium supplement material A8 of Example 8 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 26.4 ⁇ m, and the thickness of the lithium carbonate layer was 26 nm.
- a dispersion liquid take 0.2 g of multi-walled carbon nanotubes with a diameter of 20 nm and a length of 30 ⁇ m, add 25 g of silicone oil, and stir at 200 °C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion;
- the second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A9.
- the lithium supplement material A9 of Example 9 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically a lithium carbonate layer).
- the multi-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 27.6 ⁇ m, and the thickness of the lithium carbonate layer was 22 nm.
- a dispersion solution Take 0.05g of single-walled carbon nanotubes with a diameter of 2nm and a length of 30 ⁇ m, add 25g of silicone oil, and stir at 200°C until the single-walled carbon nanotubes are fully dispersed to obtain a second dispersion; under high-speed stirring conditions, The second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A10.
- the lithium supplement material A10 of Example 10 includes metallic lithium particles, single-walled carbon nanotubes, and a passivation layer (specifically, a lithium carbonate layer).
- the single-walled carbon nanotubes include built-in sections embedded in metallic lithium particles and located in the metallic lithium particles. The exposed section outside the particles; the lithium carbonate layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 28.2 ⁇ m, and the thickness of the lithium carbonate layer was 18 nm.
- a dispersion Take 0.05g of carbon fiber with a diameter of 180nm and a length of 20 ⁇ m, add 25g of silicone oil, and stir at 200°C until the carbon fibers are fully dispersed to obtain a second dispersion; under high-speed stirring, slowly add the second dispersion to the first A dispersion liquid is mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A11.
- the lithium supplement material A11 of Example 11 includes metallic lithium particles, carbon fibers, and a passivation layer (specifically, a lithium carbonate layer).
- the carbon fiber includes a built-in section embedded in the metallic lithium particles and an exposed section located outside the metallic lithium particles; lithium carbonate The layer is located on the surface of the metallic lithium particles. It was found that the average particle size of the metal lithium particles was 37.8 ⁇ m, and the thickness of the lithium carbonate layer was 25 nm.
- a dispersion Take 0.05g of graphene with a thickness of 10nm and a length of 8 ⁇ m, add 25g of silicone oil, and stir at 200°C until the graphene is fully dispersed to obtain a second dispersion; under high-speed stirring, slowly add the second dispersion The first dispersion liquid is mixed uniformly, carbon dioxide gas is introduced, stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain lithium supplement material A12.
- the lithium supplement material A12 of Embodiment 12 includes metallic lithium particles, graphene, and a passivation layer (specifically, a lithium carbonate layer), and the graphene includes a built-in section embedded in the metallic lithium particles and an exposed section located outside the metallic lithium particles;
- the lithium carbonate layer is located on the surface of the metallic lithium particles. It was found that the average particle size of the metal lithium particles was 41.0 ⁇ m, and the thickness of the lithium carbonate layer was 24 nm.
- a dispersion liquid take 0.05g of multi-walled carbon nanotubes with a diameter of 10nm and a length of 50 ⁇ m, add 25g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion;
- the second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, the stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain the lithium supplement material A13.
- the lithium supplement material A13 of Embodiment 13 includes metallic lithium particles and multi-walled carbon nanotubes, the multi-walled carbon nanotubes are partially embedded in the metallic lithium particles, and the multi-walled carbon nanotubes may include built-in segments embedded in the metallic lithium particles and The exposed section located outside the lithium metal particles. It was found that the average particle size of the metal lithium particles was 27.7 ⁇ m.
- a dispersion liquid take 0.05g of multi-walled carbon nanotubes with a diameter of 10nm and a length of 50 ⁇ m, add 25g of silicone oil, and stir at 200°C until the multi-walled carbon nanotubes are fully dispersed to obtain a second dispersion;
- the second dispersion liquid is slowly added to the first dispersion liquid and mixed uniformly, the inert gas containing fluorine gas is introduced, the stirring and heating are stopped, and the solid product is collected and dried after cooling to room temperature to obtain the lithium supplement material A14.
- the lithium supplement material A14 of Example 14 includes metallic lithium particles, multi-walled carbon nanotubes, and a passivation layer (specifically, a lithium fluoride layer), the multi-walled carbon nanotubes are partially embedded in the metallic lithium particles, and the multi-walled carbon nanotubes It may include a built-in section buried in the lithium metal particles and an exposed section located outside the lithium metal particles; the passivation layer is located on the surface of the lithium metal particles. It was found that the average particle size of the metal lithium particles was 28 ⁇ m, and the thickness of the passivation layer was 34 nm.
- the lithium supplement material D1 includes lithium metal particles and a lithium carbonate passivation layer on the surface of the lithium metal particles, wherein the average particle size of the lithium metal particles is 24.8 ⁇ m, and the thickness of the lithium carbonate layer is 19 nm.
- the lithium material D1 of Comparative Example 1 was used as a raw material, and it was physically mixed with carbon nanotubes in a weight ratio of 1:0.008.
- the carbon nanotubes were multi-walled carbon nanotubes with a diameter of 20 nm and a length of 30 ⁇ m, which were obtained as a comparison
- the lithium supplement material D2 of Comparative Example 2 includes the aforementioned lithium material D1 and multi-wall carbon nanotubes. Among them, the multi-wall carbon nanotubes and the lithium material D1 are only a simple physical mixing relationship, and the multi-wall carbon nanotubes are not partially embedded in the lithium material D1. in.
- the first dispersion add 0.05g of acetylene black with an electronic conductivity of ⁇ 100s/cm to 25g of silicone oil, stir and fully disperse at 200°C to obtain the second dispersion; under the condition of high-speed stirring, the second dispersion
- the first dispersion liquid was slowly added and mixed uniformly, carbon dioxide gas was introduced, the stirring and heating were stopped, and the solid product was collected and dried after cooling to room temperature to obtain the lithium supplement material D3 as a comparison.
- the lithium supplement materials A1 to A14 obtained in Examples 1 to 14 and the lithium supplement materials D1, D2, D3 obtained in Comparative Examples 1 to 3 were respectively prepared into lithium ion batteries, and the preparation methods were as follows:
- the lithium-ion battery obtained above was allowed to stand for 12 hours and then subjected to a lithium supplement efficiency test.
- the lithium supplement efficiency test conditions were: under normal temperature conditions, the blue power test system produced by Wuhan Landian Electronics Co., Ltd. was used to constantly charge to 3V with a current of 0.01C. And calculate the actual lithium replenishment efficiency according to the charging capacity.
- the test results are listed in Table 1.
- Example 5 1.214 70.4
- Example 6 1.185 68.7
- Example 7 1.383 80.2
- Example 8 1.361 78.9
- Example 9 1.285 74.5
- Example 10 1.251 72.5
- Example 11 1.211 70.2
- Example 12 1.066 61.8
- Example 13 1.175 68.1
- Example 14 1.199 69.5 Comparative example 1 0.818 47.4 Comparative example 2 0.857 49.7 Comparative example 3 0.836 48.5
- the lithium supplement material of the embodiment of the present disclosure has excellent lithium supplement efficiency
- the lithium supplement material (Comparative Example 1) that is not doped with conductive material and the supplement made by simply mixing the conductive material and metal lithium particles Compared with the lithium material (Comparative Example 2), the lithium ion battery containing the lithium supplement material of the embodiment of the present disclosure has higher charging capacity and higher lithium supplement efficiency.
- the conductive material in the lithium supplement material prepared by the method of the present disclosure is buried in the metal lithium particles, and after the lithium supplement material and the non-lithium negative electrode sheet are rolled, the conductive material therein can be It is closely connected with the negative electrode active material to form a vertical three-dimensional conductive network, which can not only realize the electronic conduction between the lithium metal particles and the solid phase interface of the negative electrode material, but also realize the electronic conduction between the metal lithium particles and the negative electrode active material through the conductive material.
- the electron conduction channel is also helpful for the transmission of lithium ions, and the rapid insertion process of lithium ions is realized, so that the efficiency of replenishing lithium is significantly improved, thereby effectively inhibiting the formation of dead lithium.
- Example 1 Compared the data of Example 1 and Examples 11-12 in Table 1, it can be found that when the conductive material is carbon nanotubes, the button battery has a higher charge capacity and lithium replenishment efficiency. Comparing the data of Example 1 and Examples 4-6 in Table 1, it can be found that when the diameter of the multi-walled carbon nanotubes in the lithium supplement material is 10-30nm and the length is 30-50 ⁇ m, the button cell has higher performance. The charging capacity and the efficiency of replenishing lithium.
- Example 13 Comparing the data of Example 1 and Example 13 in Table 1, it can be found that when the lithium supplement material does not have a passivation layer (Example 13), because metal lithium easily reacts with oxygen, carbon dioxide, and moisture in the air, it will A part of the active lithium is consumed, resulting in a decrease in the efficiency of replenishing lithium of the battery.
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Abstract
Description
实施/对比例 | 充电容量(mAh) | 补锂效率(%) |
实施例1 | 1.270 | 73.6 |
实施例2 | 1.125 | 65.2 |
实施例3 | 1.116 | 64.7 |
实施例4 | 1.297 | 75.2 |
实施例5 | 1.214 | 70.4 |
实施例6 | 1.185 | 68.7 |
实施例7 | 1.383 | 80.2 |
实施例8 | 1.361 | 78.9 |
实施例9 | 1.285 | 74.5 |
实施例10 | 1.251 | 72.5 |
实施例11 | 1.211 | 70.2 |
实施例12 | 1.066 | 61.8 |
实施例13 | 1.175 | 68.1 |
实施例14 | 1.199 | 69.5 |
对比例1 | 0.818 | 47.4 |
对比例2 | 0.857 | 49.7 |
对比例3 | 0.836 | 48.5 |
Claims (15)
- 一种补锂材料,其特征在于,该补锂材料包括金属锂颗粒和导电材料,所述导电材料包括埋入所述金属锂颗粒中的内置段和位于所述金属锂颗粒外部的外露段;所述导电材料的电子导电率大于100s/cm。
- 根据权利要求1所述的补锂材料,其中,所述导电材料为碳材料;所述碳材料选自碳纳米管、碳纤维和石墨烯中的至少一种;优选地,所述碳材料为碳纳米管;所述碳纳米管为单壁碳纳米管和/或多壁碳纳米管,优选为多壁碳纳米管。
- 根据权利要求2所述的补锂材料,其中,所述碳纳米管的管径为5nm-100nm,优选为10nm-30nm;所述碳纳米管的长度为10μm-80μm,优选为30μm-50μm。
- 根据权利要求1所述的补锂材料,其中,相对于100重量份的所述金属锂颗粒,所述导电材料的含量为0.1-3重量份,优选为0.5-1重量份。
- 根据权利要求1所述的补锂材料,其中,所述金属锂颗粒的平均粒径为20μm-40μm。
- 根据权利要求1所述的补锂材料,其中,所述金属锂颗粒的表面具有钝化层;所述钝化层含有碳酸锂、氟化锂和石蜡中的至少一种。
- 根据权利要求6所述的补锂材料,其中,所述钝化层的厚度为5nm-100nm。
- 一种制备补锂材料的方法,其特征在于,该方法包括:S1、在金属锂熔融的温度下,将含有熔融金属锂的第一分散液与含有导电材料的第二分散液混合,得到混合后的物料;所述导电材料的电子导电率大于 100s/cm;S2、将所述混合后的物料冷却至金属锂凝固,并进行固液分离,得到补锂材料。
- 根据权利要求8的方法,其中,所述金属锂与所述导电材料的重量比为100:(0.1-3),优选为100:(0.5-1)。
- 根据权利要求8的方法,其中,所述第一分散液中还含有表面活性剂;所述表面活性剂选自聚乙烯吡咯烷酮、十二烷基苯磺酸钠和十六烷基三甲基溴化胺的至少一种,优选为聚乙烯吡咯烷酮。
- 根据权利要求10的方法,其中,所述金属锂和所述表面活性剂的重量比为1:(0.002-0.05),优选为1:(0.005-0.02)。
- 根据权利要求8的方法,其中,所述第一分散液和所述第二分散液的分散介质为惰性有机溶剂,所述第一分散液和所述第二分散液的分散介质各自独立地选自烃、酯、醚和硅油的至少一种。
- 根据权利要求8的方法,其中,所述第一分散液和所述第二分散液的体积比为1:(0.1-10),优选为1:(0.5-3)。
- 根据权利要求8-13中任意一项所述的方法,其中,该方法还包括:步骤S1中,待所述第一分散液和所述第二分散液混合后通入二氧化碳。
- 一种锂离子电池,其特征在于,所述锂离子电池的负极包括集流体、负极活性材料和根据权利要求1-7中任意一项所述的补锂材料。
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CN113782823A (zh) * | 2021-08-12 | 2021-12-10 | 浙江锋锂新能源科技有限公司 | 一种用于固态锂电池的补锂功能电解质膜的制备方法 |
CN116773607A (zh) * | 2023-08-24 | 2023-09-19 | 宁德时代新能源科技股份有限公司 | 补锂量的检测方法和设备 |
WO2024073001A1 (en) * | 2022-09-28 | 2024-04-04 | Applied Materials, Inc. | Alkali metal oxide and hydroxide reduction in the film by ex¬ situ surface passivated layer |
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CN114975858A (zh) * | 2022-06-17 | 2022-08-30 | 珠海冠宇电池股份有限公司 | 一种负极片和应用该负极片的补锂方法 |
CN116053708B (zh) * | 2023-03-29 | 2023-07-04 | 安迈特科技(北京)有限公司 | 一种用于锂电池的补锂复合隔膜、锂电池及其制备方法 |
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CN113782823B (zh) * | 2021-08-12 | 2023-07-04 | 浙江锋锂新能源科技有限公司 | 一种用于固态锂电池的补锂功能电解质膜的制备方法 |
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JP2023506269A (ja) | 2023-02-15 |
US20230023215A1 (en) | 2023-01-26 |
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