CN112713275B - Positive electrode lithium supplementing additive and preparation method thereof - Google Patents
Positive electrode lithium supplementing additive and preparation method thereof Download PDFInfo
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- CN112713275B CN112713275B CN202011608703.4A CN202011608703A CN112713275B CN 112713275 B CN112713275 B CN 112713275B CN 202011608703 A CN202011608703 A CN 202011608703A CN 112713275 B CN112713275 B CN 112713275B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 provides a positive electrode lithium supplementing additive and a preparation method thereof. The preparation method comprises the following steps: melting metallic lithium under vacuum condition, mixing with a porous carbon material, and allowing the molten lithium to infiltrate into pores of the porous carbon material under heating condition; and after the molten lithium is completely infiltrated, introducing a reaction gas to react, and cooling under a protective atmosphere after the reaction is finished to obtain the positive electrode lithium supplementing additive. The positive electrode lithium supplementing additive has high stability, high pre-lithiation efficiency, good electronic conductivity and high compatibility with the existing lithium ion battery manufacturing process.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a positive electrode lithium supplementing additive and a preparation method thereof.
Background
Lithium ion batteries are one of the most important components of new energy automobiles, and in order to meet the rapid development demands of electric automobiles, the next generation of advanced electrode active materials having higher weight and volume capacities are required to be developed to achieve higher weight and volume energy densities. However, most of these materials suffer from excessive loss of active lithium in the first cycle. In the first-week charging process, active lithium in the positive electrode generates irreversible side reaction on the surface of the negative electrode to form a solid electrolyte interface layer (SEI), and the solid electrolyte interface layer (SEI) cannot be reversibly returned to the positive electrode in the subsequent discharging process. In general, consumption of active lithium in the positive electrode results in irreversible reduction of battery capacity, shortening of cycle life, and reduction of first-week efficiency. The irreversible consumption of the lithium source of the positive electrode in the primary charging exceeds 10 percent, and the initial cycle coulomb efficiency is lower than 90 percent. Therefore, it is necessary to introduce an additional active lithium source into the battery to compensate for the irreversible consumption of positive active lithium. Pre-lithiation is considered to be a very attractive technique by which the reversible capacity of the battery can be increased, the battery cycle life prolonged, and the battery's first week coulombic efficiency improved. There are many technological studies of prelithiation including electrochemical prelithiation and chemical prelithiation, prelithiation additives and metallic lithium prelithiation.
CN107819113a discloses a lithium supplementing additive, and its preparation method and application, the lithium supplementing additive is a core-shell structure, its core material is conductive carbon material, the shell material is lithium oxide, the lithium oxide is deposited on the surface of the conductive carbon material, and nano-scale lithium oxide particles are used to form nano-layer shell. The preparation method comprises the following steps: (1) Uniformly mixing a conductive carbon material with a lithium source to prepare a mixture; (2) Heating the mixture under reduced pressure for 30min-50h under the condition that the vacuum degree is not higher than-60 KPa and the heating temperature is 600-700 ℃; (3) After the decompression heating is finished, when the temperature is naturally cooled to 30-50 ℃, introducing dry gas without carbon dioxide for breaking the air; (4) And after the air break, drying the product to obtain the lithium supplementing additive.
CN109309220a discloses a lithium-supplementing porous silicon monoxide negative electrode material for lithium ion battery and its preparation method, the lithium-supplementing porous silicon monoxide negative electrode material has core-shell structure, the core is porous silicon monoxide, the shell is nitrogen-doped carbon material, and its thickness is 50-500 nm. The preparation method comprises the steps of adding silicon monoxide and nano metal into a ball mill to obtain a silicon monoxide alloy material A; placing the silicon monoxide alloy material A into a vacuum heat treatment furnace, and heating and reacting to obtain a porous silicon monoxide material B; naturally cooling the porous silicon monoxide material B, then introducing carbon source gas and nitrogen source gas, and cooling after reaction to obtain a porous silicon monoxide composite material C; mixing the porous silicon monoxide composite material C with inert lithium powder, adding the mixture into a ball mill, and ball milling under inert atmosphere to obtain the lithium supplementing porous silicon monoxide composite material D, namely the lithium supplementing porous silicon monoxide negative electrode material.
In the existing prelithiation technology, the used materials are high in activity, poor in stability, sensitive to oxygen and moisture, high in environmental requirements in the transportation and use processes, incapable of being stored in air for a long time and poor in compatibility with the existing mature lithium ion battery processing technology. The existing lithium supplementing additive has low pre-lithiation efficiency and cannot fully utilize lithium ions introduced by the existing lithium supplementing additive. In addition, the introduction of lithium-supplementing materials with poor conductivity may also cause an increase in the cell impedance, while lithium-supplementing materials containing dissimilar metals have the risk of metal dissolution.
Disclosure of Invention
In order to solve the technical problems, the invention provides the positive electrode lithium supplementing additive and the preparation method thereof, wherein the positive electrode lithium supplementing additive has high stability, high pre-lithiation efficiency, good electronic conductivity and high compatibility with the existing lithium ion battery manufacturing process.
In order to achieve the technical effects, the invention adopts the following technical scheme:
it is an object of the present invention to provide a positive electrode lithium supplementing additive comprising a porous carbon material and an inorganic lithium compound distributed inside the porous carbon material.
According to the invention, the inorganic lithium compound is distributed in the porous carbon material, so that the actual utilization rate of the lithium supplement additive, the chemical stability of the lithium supplement additive and the electronic conductivity of the lithium supplement additive can be effectively improved, and the main reason is that the special structure of the porous carbon material coated with the inorganic lithium compound can ensure that each inorganic lithium compound particle can be connected into a conductive network, and lithium ions are released in the charging process, so that the actual utilization rate of the lithium supplement additive is improved. In addition, the outer carbon material can isolate air and moisture, so that the chemical stability of the lithium supplementing additive is obviously improved.
As a preferred embodiment of the present invention, the porous carbon material includes any one or a combination of at least two of carbon fiber, carbon nanotube, activated carbon, ketjen black, super P, acetylene black or hollow carbon sphere with a porous structure, and typical but non-limiting examples of the combination are: a combination of carbon fiber and carbon nanotube, a combination of carbon nanotube and activated carbon, a combination of activated carbon and ketjen black, a combination of ketjen black and super P, a combination of super P and acetylene black, a combination of acetylene black and hollow carbon sphere, a combination of hollow carbon sphere and carbon fiber or a combination of carbon fiber, carbon nanotube and activated carbon, and the like.
In a preferred embodiment of the present invention, the pore diameter of the porous carbon material is 5nm to 10. Mu.m, for example, 10nm, 20nm, 50nm, 100nm, 200nm, 500nm, 1. Mu.m, 2. Mu.m, 5. Mu.m, 8. Mu.m, etc., but the pore diameter is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical range are equally applicable.
Preferably, the porous carbon material has a pore volume of 0.40 to 2.80ml/g, such as 0.50ml/g, 0.60ml/g, 0.80ml/g, 1.00ml/g, 1.20ml/g, 1.50ml/g, 1.80ml/g, 2.00ml/g, 2.20ml/g, 2.50ml/g, or 2.70ml/g, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the specific surface area of the porous carbon material is 103 to 2230m2/g, such as 150m2/g, 200m2/g, 500m2/g, 800m2/g, 1000m2/g, 1200m2/g, 1500m2/g, 1800m2/g, 2000m2/g, 2200m2/g, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the content of the porous carbon material in the lithium supplementing additive is 15 to 70wt%, such as 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the inorganic lithium compound includes any one or a combination of at least two of lithium nitride, lithium azide, lithium oxide, lithium peroxide, or lithium carbonate, and typical but non-limiting examples of the combination are: a combination of lithium nitride and lithium azide, a combination of lithium azide and lithium oxide, a combination of lithium oxide and lithium peroxide, a combination of lithium peroxide and lithium carbonate, a combination of lithium carbonate and lithium nitride or a combination of lithium nitride, lithium oxide and lithium carbonate, and the like.
Preferably, the particle size of the inorganic lithium compound is 0.8nm to 10. Mu.m, such as 1nm, 2nm, 5nm, 10nm, 20nm, 50nm, 100nm, 200nm, 500nm, 800nm, 1. Mu.m, 2. Mu.m, 5. Mu.m, or 8. Mu.m, etc., but not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
As a preferable technical scheme of the invention, the actual utilization rate of the lithium supplementing additive is more than 70%.
As a preferable technical scheme of the invention, the oxidative decomposition potential of the inorganic lithium compound in the lithium supplementing additive needs to be lower than the lithium removing potential of the positive electrode material, and the lithium intercalation potential needs to be higher than the lithium intercalation potential of the positive electrode material.
The second object of the present invention is to provide a method for preparing the positive electrode lithium-supplementing additive, which comprises the following steps:
melting metallic lithium under vacuum condition, mixing with a porous carbon material, and allowing the molten lithium to infiltrate into pores of the porous carbon material under heating condition;
and after the molten lithium is completely infiltrated, introducing a reaction gas to react, and cooling under a protective atmosphere after the reaction is finished to obtain the positive electrode lithium supplementing additive.
In a preferred embodiment of the present invention, the heating temperature is 180 to 500 ℃, such as 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, or the like, but the heating temperature is not limited to the values listed, and other values not listed in the range are equally applicable.
As a preferred embodiment of the present invention, the reaction gas includes any one or a combination of at least two of nitrogen, oxygen or carbon dioxide, and typical but non-limiting examples of the combination are: a combination of nitrogen and oxygen, a combination of oxygen and carbon dioxide, a combination of carbon dioxide and nitrogen, or a combination of nitrogen, oxygen and carbon dioxide, etc.
Preferably, the introducing rate of the reaction gas is 0.5-1.5 m 3 /min, e.g. 0.6m 3 /min、0.7m 3 /min、0.8m 3 /min、0.9m 3 /min、1.0m 3 /min、1.1m 3 /min、1.2m 3 /min、1.3m 3 /min or 1.4m 3 For example,/min, etc., but are not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the reaction time is 5 to 60min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the protective atmosphere comprises argon and/or helium.
As a preferable technical scheme of the invention, the preparation method of the positive electrode lithium supplementing additive comprises the following steps:
melting metal lithium under vacuum condition, mixing with porous carbon material, and making molten lithium infiltrate into the pores of the porous carbon material under 180-500 ℃;
after the molten lithium is completely infiltrated, the rate is 0.5 to 1.5m 3 And introducing reaction gas for reaction for 5-60 min, and cooling under a protective atmosphere after the reaction is finished to obtain the positive electrode lithium supplementing additive.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a positive electrode lithium supplementing additive and a preparation method thereof, wherein the positive electrode lithium supplementing additive has high stability, high pre-lithiation efficiency and good electronic conductivity, and has high compatibility with the existing lithium ion battery manufacturing process.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a positive electrode lithium supplementing additive, which comprises the following steps:
heating metallic lithium to 180 ℃ under vacuum condition for melting, and mixing with a pore diameter of 5nm, a pore volume of 0.4ml/g and a specific surface area of 2230m 2 Mixing/g of carbon nanotubes, and heating to 300 ℃ at a rate of 2 ℃/min to enable molten lithium to permeate into pores of the porous carbon material;
after the infiltration of the molten lithium is complete, at a rate of 1m 3 And introducing nitrogen for reaction for 60min, and cooling under argon atmosphere after the reaction is finished to obtain the positive electrode lithium supplement additive, wherein the content of the porous carbon material in the positive electrode lithium supplement additive is 70wt%.
Example 2
The embodiment provides a preparation method of a positive electrode lithium supplementing additive, which comprises the following steps:
heating metallic lithium to 180 ℃ under vacuum condition for melting, and mixing with a pore diameter of 10 μm, a pore volume of 2.8ml/g and a specific surface area of 103m 2 Mixing/g of carbon nanotubes, and heating to 250 ℃ at a rate of 2 ℃/min to enable molten lithium to permeate into pores of the porous carbon material;
after the infiltration of the molten lithium is complete, at a rate of 1m 3 And introducing nitrogen for reaction for 10min, and cooling under argon atmosphere after the reaction is finished to obtain the positive electrode lithium supplement additive, wherein the content of the porous carbon material in the positive electrode lithium supplement additive is 20wt%.
Example 3
The embodiment provides a preparation method of a positive electrode lithium supplementing additive, which comprises the following steps:
heating metallic lithium to 180 ℃ under vacuum condition for melting, and mixing with a pore diameter of 10 μm, a pore volume of 2.8ml/g and a specific surface area of 103m 2 Mixing/g of carbon nanotubes, and heating to 300 ℃ at a rate of 2 ℃/min to enable molten lithium to permeate into pores of the porous carbon material;
after the infiltration of the molten lithium is complete, at a rate of 1m 3 And introducing oxygen for reaction for 30min, and cooling in an argon atmosphere after the reaction is finished to obtain the positive electrode lithium supplement additive, wherein the content of the porous carbon material in the positive electrode lithium supplement additive is 15wt%.
Example 4
The embodiment provides a preparation method of a positive electrode lithium supplementing additive, which comprises the following steps:
heating metallic lithium to 180 ℃ under vacuum condition for melting, and mixing with pore diameter of 10 μm, pore volume of 2.6ml/g and specific surface area of 159m 2 Mixing/g of carbon nanotubes, and heating to 300 ℃ at a rate of 2 ℃/min to enable molten lithium to permeate into pores of the porous carbon material;
after the infiltration of the molten lithium is complete, at a rate of 1m 3 Introducing nitrogen gas for reaction for 10min, and cooling under argon atmosphere after the reaction is finished to obtain the positive electrode lithium supplement additive, wherein the content of the porous carbon material in the positive electrode lithium supplement additive is 23wt％。
Comparative example 1
In this comparative example, lithium nitride (uncoated carbon material) having a particle diameter of 1 to 50 μm was used as a comparative material.
Positive electrode sheets (NCM: ad: PVDF: sp=89:1:5:5) were prepared with the lithium supplement additives and the comparative materials (abbreviated as Ad) provided in examples 1 to 4 in an addition ratio of 1%, and assembled button cell batteries were tested using a graphite negative electrode (graphite: CMC: sp=8:1:1) as a counter electrode. The results are shown in Table 1.
TABLE 1
According to the test results of Table 1, the lithium supplement additives used in examples 1-4 have high utilization rate, good lithium supplement effect, and obvious improvement effect on initial efficiency and cycle of the battery, and can be completely compatible with the existing lithium battery processing and manufacturing technology
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The positive electrode lithium supplementing additive is characterized by comprising a porous carbon material and inorganic lithium compounds distributed in the porous carbon material, wherein the pore diameter of the porous carbon material is 5-100 nm, the pore volume of the porous carbon material is 0.40-1.0 ml/g, and the specific surface area of the porous carbon material is 1000-2230 m 2 And/g, wherein the particle size of the inorganic lithium compound is 0.8 nm-10 mu m;
the content of the porous carbon material in the lithium supplementing additive is 50-70 wt%;
the positive electrode lithium supplementing additive is prepared according to the following method:
melting metallic lithium under vacuum condition, mixing with a porous carbon material, and allowing the molten lithium to infiltrate into pores of the porous carbon material under heating condition;
after the molten lithium is completely infiltrated, introducing reaction gas to react, and cooling under a protective atmosphere after the reaction is finished to obtain the positive electrode lithium supplementing additive; the introducing rate of the reaction gas is 0.5-1.5 m 3 A/min; the reaction time is 5-60 min.
2. The lithium supplement additive according to claim 1, wherein the porous carbon material comprises any one or a combination of at least two of carbon fibers, carbon nanotubes, activated carbon, ketjen black, super P, acetylene black, or hollow carbon spheres of porous structure.
3. The lithium supplement additive according to claim 1, wherein the inorganic lithium compound comprises any one or a combination of at least two of lithium nitride, lithium azide, lithium oxide, lithium peroxide, or lithium carbonate.
4. The lithium supplement additive of claim 1, wherein the actual utilization of the lithium supplement additive is greater than 70%.
5. The lithium-supplementing additive according to claim 1, wherein the oxidative decomposition potential of the inorganic lithium compound in the lithium-supplementing additive is required to be lower than the delithiation potential of the positive electrode material, and the intercalation potential is required to be higher than the intercalation potential of the positive electrode material.
6. A method of preparing the positive electrode lithium-compensating additive of any of claims 1-5, comprising:
melting metallic lithium under vacuum condition, mixing with a porous carbon material, and allowing the molten lithium to infiltrate into pores of the porous carbon material under heating condition;
after the molten lithium is completely infiltrated, introducing reaction gas to react, and cooling under a protective atmosphere after the reaction is finished to obtain the positive electrode lithium supplementing additive; the introducing rate of the reaction gas is 0.5-1.5 m 3 A/min; the reaction time is 5-60 min.
7. The method according to claim 6, wherein the heating temperature is 180 to 500 ℃.
8. The method of claim 6, wherein the reactant gas comprises any one or a combination of at least two of nitrogen, oxygen, or carbon dioxide.
9. The method of claim 6, wherein the protective atmosphere comprises argon and/or helium.
10. The method of manufacturing according to claim 6, characterized in that the method of manufacturing comprises:
melting metal lithium under vacuum condition, mixing with porous carbon material, and making molten lithium infiltrate into the pores of the porous carbon material under 180-500 ℃;
after the molten lithium is completely infiltrated, the rate is 0.5 to 1.5m 3 And introducing reaction gas for reaction for 5-60 min, and cooling under a protective atmosphere after the reaction is finished to obtain the positive electrode lithium supplementing additive.
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| CN115692696A (en) * | 2021-07-30 | 2023-02-03 | 深圳市德方创域新能源科技有限公司 | Binary lithium supplement additive and preparation method and application thereof |
| CN113793983A (en) * | 2021-08-09 | 2021-12-14 | 恒大新能源技术(深圳)有限公司 | Lithium supplement additive and preparation method and application thereof |
| CN116002764B (en) * | 2021-10-27 | 2023-12-29 | 深圳市德方创域新能源科技有限公司 | Lithium supplementing additive, preparation method and application thereof |
| CN117125726A (en) * | 2023-09-20 | 2023-11-28 | 广州凌顶能源科技有限公司 | Preparation method of lithium supplementing agent, lithium supplementing agent obtained by method and application of lithium supplementing agent |
| CN117174884A (en) * | 2023-11-02 | 2023-12-05 | 宁德时代新能源科技股份有限公司 | Composite lithium supplementing material and preparation method thereof, positive electrode plate, battery and power utilization device |
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