CN114388866A - Electrolyte and metal lithium battery - Google Patents
Electrolyte and metal lithium battery Download PDFInfo
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- CN114388866A CN114388866A CN202111517720.1A CN202111517720A CN114388866A CN 114388866 A CN114388866 A CN 114388866A CN 202111517720 A CN202111517720 A CN 202111517720A CN 114388866 A CN114388866 A CN 114388866A
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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
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
Abstract
The invention relates to an electrolyte, which comprises a carbonate solvent, lithium salt and an additive, wherein the additive comprises caffeic acid, and the additive also comprises at least one of ethylene carbonate, tripropargyl phosphate and tetravinylsilane. The additive containing caffeic acid is added into the electrolyte, and the phenolic hydroxyl in the caffeic acid structure has excellent adsorption capacity on the lithium metal cathode, so that the contact between the electrolyte and active metal lithium can be avoided, and the rapid attenuation of coulomb efficiency caused by the excessive consumption of the electrolyte can be effectively avoided; the carbon-carbon double bond in the caffeic acid structure can generate in-situ anion polymerization reaction on the surface of the lithium metal negative electrode to form an SEI film rich in flexibility, the phenomenon that the SEI film generates defects under the action of mechanical stress can be improved, growth of lithium dendrites is favorably inhibited, the probability that the lithium dendrites cause short circuit or even fire explosion in a power generation battery is reduced, and the safety of the metal lithium battery is improved.
Description
Technical Field
The invention relates to the field of metal lithium ion batteries, in particular to an electrolyte and a metal lithium battery.
Background
The lithium metal has ultrahigh theoretical specific capacity (3860mAh/g), lower electrochemical potential (-3.4Vvs. standard hydrogen electrode) and lower density (0.534 g/cm)3) Thus becoming an anode material which is favored by scientific researchers. While the progress of commercialization has been hampered by uncontrolled lithium dendrite growth and the low coulombic efficiency of lithium metal anodes, the major failure modes of batteries for lithium metal anode systems are: 1. the uneven deposition of metallic lithium leads to the formation of lithium dendrites which trigger short circuits and even fire explosions in the battery; 2. the lithium metal reacts with the electrolyte to cause low coulombic efficiency and poor cycle life of the battery.
Researchers have taken various approaches over the past 40 years to improve the growth of lithium dendrites and the compatibility of lithium metal with electrolytes, such as using solid electrolytes, optimizing the components of the electrolytes, building artificial SEI films and polymer coatings, and designing three-dimensional lithium host materials. Of the many methods, electrolyte composition optimization is most economical and works well.
The electrolyte additive, which is the most important means for optimizing electrolyte components and improving battery performance, can improve uniform lithium deposition and cycle performance of a lithium metal battery by enhancing a solid electrolyte interface film (SEI interface film). The defects of the SEI film are the main causes of lithium dendrite growth, excessive consumption of the electrolyte, and rapid decay of coulombic efficiency. Lithium nitrate (LiNO)3) As the most important additive of the lithium metal battery electrolyte, the additive can be decomposed at a negative electrode to form a nitrogen-containing compound, and the compound can well stabilize a negative electrode interface, namely lithium nitrate can enhance an SEI (solid electrolyte interface) film, can inhibit the growth of lithium dendrites to a certain extent and can improve the condition of potential safety hazard caused by the fact that the lithium dendrites penetrate the SEI film. However, the solvents currently used in commercial electrolytes are mainly organic cyclic carbonates, linear carbonates, and organic carboxylic acid esters, and lithium nitrate has poor solubility in these conventional solvents, which results in poor flexibility of the SEI film formed on the negative electrode. During the use of the battery, the huge volume expansion of the negative electrode material can cause mechanical stress, if the flexibility of the SEI film is poor, the SEI film can generate defects under the action of the mechanical stress, so that more lithium is exposed in the electrolyte to carry out side reaction, and when lithium ions are transmitted through the defects, the defects of the SEI film gradually cause the growth of lithium dendrites, so that the excessive consumption of the electrolyte and the rapid attenuation of coulombic efficiency are caused.
Disclosure of Invention
The invention provides an electrolyte, which is added with caffeic acid, wherein the caffeic acid can effectively enhance the flexibility of an SEI (solid electrolyte interface) film, so that the growth condition of lithium dendrites and the compatibility of lithium metal and the electrolyte are improved, and the electrical property of a metal lithium battery is improved.
In one aspect, the present invention provides an electrolyte, including a carbonate solvent, a lithium salt, and an additive, wherein the additive includes caffeic acid, and the additive further includes at least one of ethylene carbonate, tripropargyl phosphate, and tetravinylsilane.
Furthermore, the mass fraction of the ethylene carbonate is 0.5-2% of the electrolyte, the mass fraction of the tripropargyl phosphate is 1-3% of the electrolyte, the mass fraction of the tetravinylsilane is 0.5-2% of the electrolyte, and the mass fraction of the caffeic acid is 0.5-2% of the electrolyte.
Further, the carbonate solvent includes at least one of ethyl methyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate.
Further, the mass fraction of the ethyl methyl carbonate is 50-70% of the electrolyte, the mass fraction of the fluoroethylene carbonate is 10-30% of the electrolyte, and the mass fraction of the difluoroethylene carbonate is 10-30% of the electrolyte.
Further, the lithium salt includes at least one of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium difluorooxalate borate, and lithium dioxalate borate.
Further, the concentration of the lithium hexafluorophosphate is 0.05-0.5mol/L, the concentration of the lithium bis (trifluoromethyl) sulfonyl imide is 1-2mol/L, the concentration of the lithium difluoro (oxalato) borate is 0.4-1mol/L, and the concentration of the lithium bis (oxalato) borate is 0.4-1 mol/L.
In another aspect, the present invention provides a lithium metal battery comprising the above electrolyte.
Compared with the prior art, the technical scheme of the invention has at least the following beneficial effects: the additive containing caffeic acid is added into the electrolyte, and the phenolic hydroxyl in the caffeic acid structure has excellent adsorption capacity on the lithium metal cathode, so that the contact between the electrolyte and active metal lithium can be avoided, and the rapid attenuation of coulomb efficiency caused by the excessive consumption of the electrolyte can be effectively avoided; the carbon-carbon double bond in the caffeic acid structure can generate in-situ anion polymerization reaction on the surface of the lithium metal negative electrode to form an SEI film rich in flexibility, the phenomenon that the SEI film generates defects under the action of mechanical stress can be improved, growth of lithium dendrites is favorably inhibited, the probability that the lithium dendrites cause short circuit or even fire explosion in a power generation battery is reduced, and the safety of the metal lithium battery is improved.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Solvent(s)
The main components of the currently commercialized electrolyte are lithium salt, solvent and additives. The solvent is mainly organic cyclic carbonate, linear carbonate and organic carboxylic ester, the organic cyclic carbonate comprises Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC); the organic linear carbonate is mainly methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC) or the like. The fluorinated organic carbonate is the most common solvent of a lithium metal electrolyte system, and can well passivate a lithium metal cathode, so that a stable SEI film is favorably formed. However, the use of a single fluorinated cyclic carbonate as a solvent results in a relatively high viscosity of the electrolyte system, which is not favorable for the performance of the lithium metal battery, and therefore the fluorinated cyclic carbonate is often used in combination with a linear carbonate solvent having a relatively low viscosity to improve the performance of the lithium metal battery.
The invention improves the existing commercialized electrolyte system, and in order to be closer to the existing commercialized electrolyte system and develop the additive suitable for the existing commercialized electrolyte system, the solvents selected in the invention are all common solvents in the electrolyte. The solvent of the invention adopts the combination of linear carbonate and fluorinated cyclic carbonate, the fluorinated cyclic carbonate has high dielectric constant but large viscosity, and the linear carbonate has low viscosity but low dielectric constant, so that the contents of the two solvents need to be reasonably regulated and controlled to meet the requirements. The inventor determines through experiments that: when the mass fraction of the linear carbonate is 50-70% of the electrolyte and the mass fraction of the fluorinated cyclic carbonate is 10-30% of the electrolyte, the electrolyte can meet the requirement of viscosity, maintain sufficient conductivity and solubility and be beneficial to SEI film formation. In this embodiment, the linear carbonate is ethyl methyl carbonate, the fluorinated cyclic carbonate is fluoroethylene carbonate or difluoroethylene carbonate, and the above solvents are all excellent electrolytes for lithium ion batteries, wherein when fluoroethylene carbonate or difluoroethylene carbonate is used as a solvent, a compact SEI film can be formed on the negative electrode, and further the electrolyte can be prevented from being further decomposed.
Lithium salt
Lithium salt dissolved in the electrolyte is more easily subjected to a reduction reaction than a solvent, the reduction product is a part of the SEI film, namely the lithium salt is also one of factors influencing the formation and performance of the SEI film, and the type and content of the lithium salt influence the formation and stability of the SEI film and further influence the performance of the battery. Lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium difluorooxalato borate, lithium dioxaoxalato borate and the like are commonly used lithium salts in the current commercial electrolyte, and the lithium hexafluorophosphate is the most commonly used lithium salt in the current electrolyte, has good compatibility with a carbonate solvent although the lithium hexafluorophosphate has poor thermal stability, and has high ionic conductivity in a nonaqueous solvent; lithium bistrifluoromethylsulfonyl imide has high solubility and conductivity, but will corrode the current collector above 3.7V; lithium difluoro (oxalato) borate has good film forming property and good compatibility with the battery anode, can form a passivation film on the surface of a current collector and inhibit the oxidation of electrolyte, but is expensive, and the production and manufacturing cost of the battery is inevitably increased when the lithium difluoro (oxalato) borate is used in the electrolyte in a large amount; lithium dioxalate borate has higher conductivity, wider electrochemical window, good thermal stability and better cycling stability, but is hardly dissolved in part of low dielectric constant solvents. The currently used lithium salts have advantages, but the single use of the lithium salts cannot meet the requirements of being used as electrolyte solutes, so that the lithium salts need to be combined and used in the electrolyte to meet the requirements of low dissociation energy, higher solubility, better stability, good SEI film forming property, good passivation effect on a current collector, low cost, no toxicity and no harm.
The invention combines the common lithium salts to make up the deficiency of single lithium salt, improve the film forming property of SEI, reduce the consumption of electrolyte in the circulation process and improve the performance of the metal lithium battery. The content of the lithium salt affects the conductivity of the electrolyte, the amount of lithium ions in the electrolyte, and further affects the performance of the metal lithium battery, so that the content of the lithium salt needs to be regulated to meet the requirements. The inventors have found through experiments that when the above lithium salts are used in combination in a combination system in which the solvent is a linear carbonate and a fluorinated cyclic carbonate, the respective concentration ranges satisfy: the concentration of lithium hexafluorophosphate is 0.05-0.5mol/L, the concentration of lithium bis (trifluoromethyl) sulfonyl imide is 1-2mol/L, the concentration of lithium difluoro (oxalato) borate is 0.4-1mol/L, and the concentration of lithium bis (oxalato) borate is 0.4-1 mol/L.
Additive agent
The invention improves the existing commercialized electrolyte system, and aims to improve the flexibility of the SEI film, thereby improving the growth condition of lithium dendrites and the compatibility of lithium metal and electrolyte so as to improve the electrical property of the lithium metal battery, so that the additive in the invention mainly has the effect of improving the performance of the electrode SEI film.
The additive comprises at least one of ethylene carbonate, tripropargyl phosphate, tetravinylsilane and caffeic acid. Ethylene carbonate is a common organic film forming additive and an overcharge protection additive, wherein the ethylene carbonate generates a polymerization reaction on the surface of a negative electrode to form a layer of compact SEI film, so that the electrolyte is prevented from further reductive decomposition on the surface of the negative electrode, but the ethylene carbonate also generates an oxidation reaction on the surface of a positive electrode, so that the performance of the lithium ion battery is negatively influenced;
the tripropargyl phosphate belongs to unsaturated phosphate compounds, can generate polymerization reaction on the surface of a negative electrode to form an SEI film so as to prevent the corrosion of hydrogen ions, and is favorable for preventing the degradation of an electrolyte;
silicon (Si) element contained in tetravinylsilane can form a solid ion-conductive film on the surfaces of the positive electrode and the negative electrode by physical adsorption and electrochemical reaction, and inhibit side reaction of the positive electrode active material under high voltage; and the contained unsaturated bonds can absorb unstable free radicals in the electrolyte, reduce side reactions and generate organic carbonate on the surface of the negative electrode to protect the negative electrode, but the impedance is high, so that the cycle performance of the lithium ion battery is influenced.
The above additives have their own advantages, but they cannot satisfy the electrochemical performance of lithium ion batteries when used alone, and thus need to be combined with additional additives.
Caffeic acid as an additive can generate mild anionic polymerization reaction at a metal lithium cathode to regulate and control the lithium deposition structure and morphology, and the specific expression is as follows: the phenolic hydroxyl contained in the lithium ion battery has excellent adsorption capacity on a lithium metal negative electrode, so that the contact between an electrolyte and active metal lithium can be avoided; the carbon-carbon double bond contained in the film can generate in-situ anion polymerization reaction on the surface of the lithium metal negative electrode to form a flexible SEI film.
For each additive, whether used alone or in combination, the amount used is significantly different from the modification effect of the electrolyte system, i.e. it can only give a significant improvement effect to the electrolyte system at the optimum amount, and the inventors have experimentally determined the amount of the above additives used in combination: the mass fraction of the ethylene carbonate is 0.5-2% of the electrolyte, the mass fraction of the tripropargyl phosphate is 1-3% of the electrolyte, the mass fraction of the tetravinyl silane is 0.5-2% of the electrolyte, and the mass fraction of the caffeic acid is 0.5-2% of the electrolyte.
Example 1
Weighing lithium salt under the protection of argon gas: 20g of lithium bistrifluoromethylsulfonyl imide, 4g of lithium difluorooxalato borate and 0.5g of lithium hexafluorophosphate; preparing a solvent: uniformly mixing 54.5g of methyl ethyl carbonate and 20g of difluoroethylene carbonate; weighing an additive: vinylene carbonate 0.5g and caffeic acid 0.5 g; adding lithium salt into a solvent, adding an additive after the lithium salt is dissolved, and uniformly stirring to obtain the electrolyte. A single-crystal high-nickel ternary material (NCM811) is used as a positive electrode, lithium metal (50 mu m) is used as a negative electrode, Polyethylene (PE) is used as a diaphragm, and the electrolyte sample prepared in the embodiment is used as an electrolyte to assemble the soft package battery.
Example 2
This example differs from example 1 only in that caffeic acid is 1g, and the remaining conditions and parameters are the same as those for example 1.
Example 3
Weighing lithium salt under the protection of argon gas: 23g of lithium bistrifluoromethylsulfonyl imide, 4g of lithium difluorooxalato borate and 0.5g of lithium hexafluorophosphate; preparing a solvent: 51.5g of methyl ethyl carbonate and 20g of difluoroethylene carbonate are uniformly mixed; weighing an additive: vinylene carbonate 0.5g and caffeic acid 0.5 g; adding lithium salt into a solvent, adding an additive after the lithium salt is dissolved, and uniformly stirring to obtain the electrolyte. A single-crystal high-nickel ternary material (NCM811) is used as a positive electrode, lithium metal (50 mu m) is used as a negative electrode, Polyethylene (PE) is used as a diaphragm, and the electrolyte sample prepared in the embodiment is used as an electrolyte to assemble the soft package battery.
Comparative example 1
This comparative example differs from example 1 only in that 15g of lithium bistrifluoromethylsulfonyl imide and 59.5g of ethyl methyl carbonate, and the other conditions and parameters are exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that fluoroethylene carbonate is replaced by fluoroethylene carbonate, and the other conditions and parameters are exactly the same as those of example 1.
Comparative example 3
The comparative example is different from example 1 only in that caffeic acid 2g and ethyl methyl carbonate content is 53g, and other conditions and parameters are completely the same as those of the example.
Comparative example 4
The comparative example is different from example 1 only in that caffeic acid is not added, the content of ethyl methyl carbonate is 55g, and other conditions and parameters are completely the same as those of example 1.
And (3) respectively carrying out a charge-discharge cycle test on the batteries for 200 weeks, wherein the test conditions meet the following conditions: constant current and voltage charging to 4.3V under the current density of 0.2C, cutoff current of 0.02C, 1C discharging to 2.75V. The test results are shown in Table 1, Table 1
| Cycle @200 at 25 ℃thCapacity retention rate | |
| Example 1 | 97.4％ |
| Example 2 | 98.2％ |
| Example 3 | 96.3％ |
| Comparative example 1 | 85.1％ |
| Comparative example 2 | 78.3％ |
| Comparative example 3 | 65.6％ |
| Comparative example 4 | 63.5％ |
As can be seen from table 1, the capacity retention rate of the lithium metal batteries prepared in examples 1 to 3 after 200 cycles at normal temperature can reach 96.3% or more, wherein the capacity retention rate of the lithium metal battery prepared in example 2 after 200 cycles is the highest and is 98.2%. The flexibility of the SEI film is enhanced by the caffeic acid added into the electrolyte system, and the caffeic acid and other components in the electrolyte act synergistically, so that the growth condition of lithium dendrites is improved, the consumption of the electrolyte is reduced, and the cycle life of the metal lithium battery is prolonged.
As can be seen from examples 1, 3 and 1, the cycle performance of the lithium metal battery is deteriorated when the content of lithium bistrifluoromethylsulfonyl imide is too high or too low; as can be seen from example 1 and comparative example 2, when the difluoroethylene carbonate is used as a co-solvent, the cycle performance of the lithium metal battery is better than that of the fluoroethylene carbonate, which may be caused by that the SEI film formed by the difluoroethylene carbonate contains more lithium fluoride (LiF), so that the passivation effect is better; it can be seen from examples 1, 2, 3 and 4 that too high and too low content of caffeic acid deteriorates the electrical performance of the battery, too low content of caffeic acid fails to effectively passivate the lithium metal negative electrode, and the solid electrolyte film formed by too high content of caffeic acid becomes thick, which leads to too large polarization of the battery and thus deterioration of the cycle performance of the metal lithium battery.
The electrolyte provided by the invention has the following advantages:
1. the invention selects common solvents to ensure that the electrolyte system of the invention has matching property and correlation with the existing commercial electrolyte system, thereby ensuring that the additive developed by the invention is suitable for the existing commercial electrolyte system;
2. by screening and combining optimization of the solvent and the lithium salt, favorable conditions are provided for SEI film formation, the SEI film formation is promoted, the stability of the SEI film formation is improved, and the electrolyte is prevented from being further decomposed, so that the cycle life of the metal lithium battery is prolonged;
3. caffeic acid is added into an electrolyte system, and the additive is combined and optimized, so that phenolic hydroxyl in a caffeic acid structure has excellent adsorption capacity on a lithium metal cathode, and the contact of the electrolyte and active metal lithium can be avoided, thereby effectively avoiding the rapid attenuation of coulomb efficiency caused by the excessive consumption of the electrolyte; carbon-carbon double bonds in the caffeic acid structure can generate in-situ anion polymerization reaction on the surface of the lithium metal negative electrode to form an SEI film with high flexibility, the phenomenon that the SEI film generates defects under the action of mechanical stress can be improved, the growth of lithium dendrites can be inhibited, the probability that the lithium dendrites cause short circuit or even fire explosion in a power generation battery is reduced, and the safety of the lithium metal battery is improved;
4. the combination optimization of the solvent, the lithium salt and the additive in the electrolyte system enhances the flexibility of the SEI film, effectively regulates and controls the lithium deposition structure and morphology, and improves the electrical property of the lithium metal anode battery system.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The electrolyte comprises a carbonate solvent, a lithium salt and an additive, wherein the additive comprises caffeic acid, and the additive further comprises at least one of ethylene carbonate, tripropargyl phosphate and tetravinylsilane.
2. The electrolyte according to claim 1, wherein the mass fraction of the ethylene carbonate is 0.5-2% of the electrolyte, the mass fraction of the tripropargyl phosphate is 1-3% of the electrolyte, the mass fraction of the tetravinylsilane is 0.5-2% of the electrolyte, and the mass fraction of the caffeic acid is 0.5-2% of the electrolyte.
3. The electrolyte of claim 1, wherein the carbonate solvent comprises at least one of ethyl methyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate.
4. The electrolyte of claim 3, wherein the mass fraction of the ethyl methyl carbonate is 50-70% of the electrolyte, the mass fraction of the fluoroethylene carbonate is 10-30% of the electrolyte, and the mass fraction of the difluoroethylene carbonate is 10-30% of the electrolyte.
5. The electrolyte of claim 1, wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium difluorooxalato borate, and lithium dioxalate borate.
6. The electrolyte of claim 5, wherein the concentration of lithium hexafluorophosphate is 0.05 to 0.5mol/L, the concentration of lithium bistrifluoromethylsulfonyl imide is 1 to 2mol/L, the concentration of lithium difluorooxalato borate is 0.4 to 1mol/L, and the concentration of lithium dioxaoxalato borate is 0.4 to 1 mol/L.
7. The electrolyte of claim 1, wherein the additives are caffeic acid and vinylene carbonate.
8. The electrolyte of claim 1, wherein the solvent comprises ethyl methyl carbonate, and the mass fraction of the ethyl methyl carbonate is 50-70% of the electrolyte.
9. The electrolyte of claim 1, wherein the lithium salt is lithium bistrifluoromethylsulfonyl imide, lithium difluorooxalato borate, lithium hexafluorophosphate.
10. A lithium metal battery, characterized in that it comprises an electrolyte according to any one of claims 1-9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
| CN115011978A (en) * | 2022-06-02 | 2022-09-06 | 杭州四马化工科技有限公司 | Preparation method of lithium difluoroborate |
| CN115084648A (en) * | 2022-07-20 | 2022-09-20 | 中南大学 | Solid electrolyte membrane and lithium metal solid battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
| CN115011978A (en) * | 2022-06-02 | 2022-09-06 | 杭州四马化工科技有限公司 | Preparation method of lithium difluoroborate |
| CN115011978B (en) * | 2022-06-02 | 2024-01-26 | 杭州四马化工科技有限公司 | Preparation method of lithium difluoro oxalate borate |
| CN115084648A (en) * | 2022-07-20 | 2022-09-20 | 中南大学 | Solid electrolyte membrane and lithium metal solid battery |
| CN115084648B (en) * | 2022-07-20 | 2023-12-15 | 中南大学 | Solid electrolyte membrane and lithium metal solid battery |
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