CN115692858A - Local high-concentration electrolyte suitable for potassium ion battery and application thereof - Google Patents
Local high-concentration electrolyte suitable for potassium ion battery and application thereof Download PDFInfo
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Abstract
The invention discloses a local high-concentration electrolyte suitable for a potassium ion battery, which consists of a high-concentration ether electrolyte and a functional fluorinated diluent, wherein the high-concentration ether electrolyte preferably consists of potassium bis (fluorosulfonyl) imide and ethylene glycol dimethyl ether, the concentration of the high-concentration ether electrolyte is 3-6 mol/L, the functional fluorinated diluent preferably consists of 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, and the volume ratio of the two is (2). The specific combination not only can obviously improve the viscosity and the fluidity of the high-concentration ether electrolyte and the electrode wettability, but also can change the solvation structure and the molecular energy level of potassium ions in the electrolyte, effectively regulate and control the formation of a solid electrolyte layer on the surface of the phosphorus/carbon cathode and improve the electrochemical reversibility, the circulation stability and the rate capability in the potassium storage process. The local high-concentration electrolyte is further applied to a potassium ion full battery consisting of a phosphorus/carbon cathode and a purified 3,4,9, 10-perylene tetracarboxylic dianhydride anode, so that long cycle life and high coulombic efficiency can be realized.
Description
Technical Field
The invention belongs to the technical field of liquid electrolyte of metal batteries, and particularly relates to local high-concentration electrolyte of a potassium ion battery and an application method thereof.
Background
Potassium ion batteries are gradually receiving important attention from the field of electrochemical energy research due to abundant reserve of potassium resources, low cost and similarity of basic physicochemical properties of potassium and lithium/sodium elements. As a cheap negative electrode material, phosphorus can perform alloy reaction with a plurality of potassium ions, so that the phosphorus has extremely high theoretical capacity and energy density, but the electrochemical performance of the phosphorus is still limited by low conductivity and large volume change rate in the potassium storage process. Although the combination with the high-conductivity/high-flexibility carbon material can buffer the huge volume change of the high-conductivity/high-flexibility carbon material in the potassium storage process to a certain extent, the prepared phosphorus/carbon (P/C) negative electrode material still faces the problems of serious internal structure collapse, severe interface side reaction, rapid electrochemical performance attenuation and the like. As an interfacial reaction byproduct during discharge, a Solid Electrolyte Interface (SEI) layer directly determines basic electrochemical properties of the P/C anode material.
In the current research, the electrolyte components are generally considered to be capable of effectively regulating and controlling the SEI layer forming process of the negative electrode material of the potassium ion battery, and simultaneously, the cycle stability of the electrolyte components is obviously improved. The potassium salt and the solvent directly determine the formation of the SEI layer of the negative electrode material and the electrochemical performance of the SEI layer as main components of the electrolyte of the potassium ion battery. From the potassium salt perspective, potassium bis-fluorosulfonylimide (KFSI) with high solubility and low Lowest Unoccupied Molecular Orbital (LUMO) level (-2.062 eV) is compared to potassium hexafluorophosphate (KPF) with low solubility and high LUMO level (-1.988 eV) 6 ) The SEI layer with more uniform coating, more complete structure, better flexibility and thinner thickness can be formed on the surface of the cathode material, and the electrochemical reversibility and the cycling stability of the cathode material in the potassium storage process are further remarkably improved. From the perspective of the solvent, the Ether (Ether) electrolyte with higher dielectric constant can effectively promote the dissociation of the potassium salt in the solvent and increase the viscosity of the electrolyteSolubility. On the basis of the above, the concentration of KFSI in the organic solvent is increased (>3M) is found to be capable of effectively reducing the LUMO energy level of the electrolyte, further enhancing the leading effect of KFSI in the SEI forming process and reducing free solvent molecules, thereby forming an SEI layer with firm structure and excellent flexibility on the surface of the high-capacity negative electrode material and obviously improving the electrochemical reversibility and stability of the high-capacity negative electrode material.
Chinese patent CN201810551120.9 reports a concentrated electrolyte system suitable for a potassium ion battery, wherein the concentration of potassium salt is more than or equal to 2mol/L, so that the battery electrode material can exert excellent electrochemical performance, and the concentrated electrolyte system can be successfully applied to the potassium ion battery assembled by a bismuth negative electrode or a p-benzoquinone organic negative electrode and a Prussian-like white positive electrode. Chinese patent CN201910675748.4 reports a high-concentration potassium ion battery electrolyte, which takes potassium bis (fluorosulfonyl imide) (KFSI) as a solute, the concentration of the potassium salt is 3-5 mol/L, a stable SEI layer can be formed on the surface of a graphite negative electrode, and the potassium storage performance and the cycle life of the battery are obviously improved.
However, the high viscosity, low fluidity, low ionic conductivity and poor electrode wettability of the high-concentration electrolyte itself will directly weaken the rate capability of the negative electrode material under high current density, and the higher production cost thereof will further hinder the commercialization process of the potassium ion battery. On the other hand, the common use of flammable and volatile active solvents in traditional organic electrolytes also puts a huge shadow on the safety of potassium ion batteries.
In view of the above disadvantages, it is necessary to provide an electrolyte capable of efficiently regulating and controlling a potassium ion battery.
Disclosure of Invention
Aiming at the defects of high viscosity, low fluidity, low ionic conductivity, poor electrode wettability and the like of high-concentration electrolyte, the invention introduces a functional fluorinated solvent as a diluent into the high-concentration ether electrolyte of the potassium ion battery, thereby forming the local high-concentration electrolyte with the solvation characteristic of the high-concentration electrolyte and the fluidization characteristic of the conventional electrolyte, and accurately constructing an SEI layer with complete structure, good flexibility and thin thickness on the surface of a P/C negative electrode material, thereby obviously improving the reversible capacity, cycle life and rate capability of the SEI layer in the potassium ion battery.
The purpose of the invention is realized by the following technical scheme.
A local high-concentration electrolyte of a potassium ion battery comprises a functional fluorinated solvent and a high-concentration ether electrolyte. Firstly, potassium salt with a certain concentration is dissolved in an ether solvent, and the solution is fully stirred for a plurality of hours to prepare high-concentration ether electrolyte. And then adding the functional fluorinated solvent into the high-concentration ether electrolyte according to a certain volume percentage, and fully stirring for a plurality of hours, thereby preparing the local high-concentration electrolyte.
Furthermore, the high-concentration ether electrolyte mainly comprises an ether solvent and potassium salt, and the concentration of the ether solvent is 3-6 mol/L.
Further, the volume ratio of the functional fluorinated solvent to the high-concentration ether electrolyte is (2,1.
Furthermore, the stirring time of the high-concentration ether electrolyte is 24-72 hours, the stirring time of the local high-concentration electrolyte is 48-96 hours, and the stirring speed is 400-800 rpm.
<xnotran> , 1,1,2,2- -2,2,3,3- , (2,2,2- ) , ( ) , (2,2,2- ) ,1H,1H,5H- 1,1,2,2- ,1- (2,2,2- ) -1,1,2,2- ,1,1,2,2- -2,2,2- , -1,1,1,3,3,3- . </xnotran> 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether is preferred.
Further, the ether solvent includes ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane.
Further, potassium salts include potassium bis (fluorosulfonyl) imide, potassium bis (trifluoromethanesulfonyl) imide, potassium hexafluorophosphate, potassium perchlorate, potassium trifluoromethanesulfonate. Potassium bis (fluorosulfonyl) imide is preferred.
A potassium ion half-cell is provided, which comprises a P/C composite electrode, a composite diaphragm, a potassium metal cathode and a local high-concentration electrolyte.
Provides a potassium ion full cell, which comprises a pre-potassified P/C composite negative electrode, a composite diaphragm, a pre-potassified 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA) positive electrode and local high-concentration electrolyte.
Further, the 3,4,9, 10-perylene tetracarboxylic dianhydride raw material is firstly treated for 3 to 6 hours at the temperature of 300 to 500 ℃ under the argon atmosphere to obtain the purified 3,4,9, 10-perylene tetracarboxylic dianhydride anode material.
Further, the 3,4,9, 10-perylenetetracarboxylic dianhydride positive electrode is composed of 60-80 wt.% of purified 3,4,9, 10-perylenetetracarboxylic dianhydride positive electrode material, 10-20 wt.% of acetylene black, and 10-20 wt.% of polyvinylidene fluoride. The components are firstly dissolved in a certain amount of N-methyl pyrrolidone, then evenly coated on aluminum foil, and vacuum driven for 12-36 hours at 70-100 ℃, thus preparing the 3,4,9, 10-perylene tetracarboxylic dianhydride anode.
Furthermore, the mass ratio of the active substances of the P/C negative electrode and the 3,4,9, 10-perylenetetracarboxylic dianhydride positive electrode is 1.
The composite diaphragm consists of a layer of conventional polymer diaphragm and a layer of glass fiber diaphragm.
The pre-potassium process is to pre-activate the P/C electrode and the PTCDA electrode in the potassium ion half cell for 3 to 5 times, then discharge the electrodes to realize pre-potassium, wherein the pre-activation current densities of the P/C electrode and the PTCDA electrode are 100 to 400 and 25 to 100mA g -1 。
Compared with the prior art, the invention has the following advantages:
according to the invention, by preparing the local high-concentration electrolyte with good fluidity and a unique solvation structure, the SEI layer with a firm structure, good flexibility and a thin thickness is successfully and controllably constructed on the surface of the high-capacity P/C cathode, so that the structure/interface stability of the electrolyte in the potassium storage process is improved, the electrochemical reversibility and the cycle stability of the electrolyte are obviously improved, and the long cycle life of the potassium ion full cell is realized. The method has the advantages of low cost, simple operation, strong adaptability and the like, and has very wide application prospect.
Drawings
FIG. 1 is a potassium ion half-cell charge-discharge curve of a P/C negative electrode of a local high-concentration electrolyte B prepared in example 2 under different current densities;
FIG. 2 is a graph showing the charge and discharge curves of a potassium ion half cell of a PTCDA positive electrode and a P/C negative electrode of a local high-concentration electrolyte B prepared in example 2;
FIG. 3 shows the cycle performance of a full potassium ion battery comprising a PTCDA positive electrode and a P/C negative electrode of a local high-concentration electrolyte B prepared in example 2;
FIG. 4 shows the full-cell rate performance of potassium ions formed by the PTCDA positive electrode and the P/C negative electrode of the local high-concentration electrolyte B prepared in example 2;
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and the process parameters not specifically mentioned may be performed with reference to conventional techniques.
Preparing a P/C composite material: the P/C composite material is mainly prepared by a high-energy ball milling method, red phosphorus and commercial porous carbon black are added into a stainless steel ball milling tank according to a certain proportion, a proper amount of stainless steel ball milling beads are added, gradient-rotating-speed high-energy ball milling is carried out after the assembly in an argon atmosphere glove box is completed, and finally, sieving, collecting and storing are carried out in the argon atmosphere glove box.
The mass ratio of phosphorus to carbon was 7. The stainless steel ball milling beads are composed of ball milling beads with the diameter of 2,3,5mm, and the mass ratio of the stainless steel ball milling beads to the stainless steel ball milling beads is 1. The mass ratio of the P/C material to the stainless steel ball is 1.
The gradient rotation speed high-energy ball milling is mainly that planetary ball milling is carried out in sequence at different rotation speeds so as to realize uniform compounding of phosphorus and carbon on a nanometer size. The high-energy planetary ball milling is carried out for 12 hours at the rotating speeds of 200 rpm, 300 rpm and 400rpm in sequence, and the process is repeated for 2 times.
Preparing a high-performance P/C negative electrode of the potassium ion battery: firstly, dispersing the P/C composite material, acetylene black and sodium alginate in a certain amount of deionized water according to a certain mass ratio to prepare electrode slurry, uniformly coating the electrode slurry on the surface of a copper foil, and drying the copper foil in vacuum at a certain temperature for a certain time.
A P/C composite material, acetylene black,the mass ratio of the sodium alginate is 7. The vacuum drying temperature of the P/C negative electrode is 60 ℃, and the drying time is 12 hours. The active material loading of the P/C negative electrode is 1.0mg cm -2 .
Example 1
Firstly, dissolving the potassium bis (fluorosulfonyl) imide salt in an ethylene glycol dimethyl ether solvent, and fully stirring for 48 hours at 600rpm to prepare a high-concentration ether electrolyte, wherein the concentration of the potassium salt in the electrolyte is 6mol/L. Then adding 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether into the high-concentration ether electrolyte, wherein the volume ratio of 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether to the high-concentration ether electrolyte is 1.
Example 2
The same procedure as in example 1 was used except that the volume ratio of 1,1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether to the high concentration ether electrolyte was 1.
Example 3
The same procedure as in example 1 was used except that the volume ratio of 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether to the high concentration ether electrolyte was 1.
Example 4
The same procedure as in example 1 was used except that the functional fluorinated solvent was 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether, to obtain a locally highly concentrated electrolyte D.
Example 5
The same procedure as in example 1 was used except that the potassium salt was potassium hexafluorophosphate, to obtain a locally high concentration electrolyte E.
Comparative example 1
Firstly, dissolving potassium bis (fluorosulfonyl) imide in an ethylene glycol dimethyl ether solvent, and fully stirring at 600rpm for 48 hours to prepare a high-concentration ether electrolyte F, wherein the concentration of potassium salt in the electrolyte is 6mol/L.
Comparative example 2
Firstly, dissolving the potassium bis (fluorosulfonyl) imide salt in an ethylene glycol dimethyl ether solvent, and fully stirring for 48 hours at 600rpm to prepare the low-concentration ether electrolyte G, wherein the concentration of the potassium salt in the electrolyte is 3mol/L.
Example 6
And (3) assembling the pre-potassized P/C composite negative electrode, the composite diaphragm, the pre-potassized PTCDA positive electrode and the local high-concentration electrolyte B in the embodiment 2 into a potassium ion full battery. PTCDA was first treated under an argon atmosphere at 450 ℃ for 4 hours. The PTCDA positive electrode consisted of 80wt.% of purified PTCDA positive electrode material, 10wt.% of acetylene black, 10wt.% of polyvinylidene fluoride. The components are firstly dissolved in a certain amount of N-methyl pyrrolidone, then evenly coated on an aluminum foil, and vacuum driving is carried out for 24 hours at the temperature of 90 ℃, thus preparing the 3,4,9, 10-perylene tetracarboxylic dianhydride anode. The active material mass ratio of the P/C negative electrode to the PTCDA positive electrode is 1. The composite diaphragm consists of a layer of celgard 2400 diaphragm and a layer of glass fiber diaphragm. The pre-potassium process comprises the steps of pre-activating a P/C electrode and a PTCDA electrode in a potassium ion half-cell for 5 times, and then discharging the electrodes to realize pre-potassium, wherein the pre-activation current densities of the P/C electrode and the PTCDA electrode are respectively 200mA g and 50mA g -1 。
The potassium ion conductivities and transference numbers of the different electrolytes prepared in examples 1 to 5 and comparative examples 1 to 2 were further compared.
TABLE 1 Potassium ion conductivities and transference numbers of different electrolytes prepared in examples 1 to 3 and comparative examples 1 to 2
Table 1 further compares the potassium ion conductivity and transference number of different electrolytes prepared in examples 1-5 and comparative examples 1-2. Wherein the low concentration electrolyte G exhibits a high conductivity for potassium ions (3.74 mS cm) -1 ) While the high concentration electrolyte F showed a lower potassium ion conductivity (1.88 mS cm) -1 ) While the addition of a certain amount of a specific functional fluorinated ether diluent is effective in improving the high concentrationThe viscosity and the fluidity of the electrolyte further improve the conductivity of the local high-concentration electrolyte A-D potassium ions to 1.96,1.94,1.92 and 1.90. However, after the specific functional fluorinated ether diluent is replaced, the potassium ion conductivity of the local high-concentration electrolyte E can be reduced to 1.65mS cm -1 . Meanwhile, the potassium ion transport number of the low concentration electrolyte F was 0.42, and the potassium ion transport number of the high concentration electrolyte was 0.28. When a certain amount of functional fluorinated ether diluent is introduced into the high-concentration electrolyte, the potassium ion migration number of the local high-concentration electrolyte A-D is remarkably increased to 0.73,0.75,0.56 and 0.52. After replacement of the specific functional fluorinated ether diluent, the local high concentration electrolyte E has a potassium ion transport number of 0.48. A comparison of the relevant parameters in table 1 further shows the excellent electrochemical properties of the locally high concentration electrolyte of a potassium ion battery.
P/C negative electrodes using different electrolytes prepared in examples 1 to 5 and comparative examples 1 to 2 at 200mA g -1 The circulation performance of the potassium ion half-cell under the current density is compared systematically, and the experimental data are shown in table 2:
further, the P/C negative electrodes using different electrolytes prepared in examples 1 to 5 and comparative examples 1 to 2 were charged at 800mA g -1 And performing systematic comparison on the cycle performance of the potassium ion half cell under the current density. The experimental data are shown in Table 3
Further investigation of specific charge capacities of P/C cathodes of different electrolytes prepared in examples 1-5 and comparative examples 1-2 after 5 cycles at different current densities is performed, the specific data are shown in Table 4
The experimental data from tables 2 to 4 show that the P/C negative electrode using the local high concentration electrolyte B of example 2 exhibits the most excellent electrochemical performance. Fig. 1 further compares the charge and discharge curves of the potassium ion half-cell using the P/C negative electrode of the local high-concentration electrolyte B prepared in example 2 at different current densities, and it is found that the P/C negative electrode material shows a significant alloying/dealloying reaction process and a relatively small electrochemical polarization phenomenon at different current densities. FIG. 2 is a charge and discharge curve of a PTCDA positive electrode and a P/C negative electrode using the localized high concentration electrolyte B prepared in example 2. Wherein the PTCDA positive electrode is at 50mA g -1 The discharge specific capacity of the current density is 138mAh g -1 While the P/C negative electrode is at 200mA g -1 Has a specific charge capacity of 728mAh g -1 . Fig. 3 shows cycle performance of all-potassium-ion batteries formed by PTCDA positive electrode and P/C negative electrode using the localized high-concentration electrolyte B prepared in example 2, wherein current density and specific capacity are calculated based on active material mass of the positive electrode material. The first discharge specific capacity of the assembled PTCDA// P/C full battery is 138mAh g -1 And at 50mA g -1 After the current is circulated for 400 times, the specific discharge capacity is 47mAh g -1 And the coulombic efficiency is still as high as 98%. Fig. 4 shows the full-cell rate performance of potassium ions formed by PTCDA positive electrode and P/C negative electrode using the localized high-concentration electrolyte B prepared in example 2, wherein the current density and specific capacity are calculated based on the mass of the active material of the positive electrode material. When the current is 50, 100, 200 and 400mA g -1 When cycled at current densities of (C), the assembled whole PTCDA// P/C battery may exhibit 123, 100, 85 and 69mAh g, respectively -1 Specific discharge capacity of (2). Even at 800mA g -1 When circulating at a current density of 39mAh g, the magnetic core can still maintain -1 The specific discharge capacity of (2).
The local high-concentration electrolyte can controllably construct an SEI layer with firm structure, good flexibility and thinner thickness on the surface of a high-capacity P/C cathode so as to improve the structure/interface stability of the electrolyte in the potassium storage process, thereby obviously improving the electrochemical reversibility and the cycle stability of the electrolyte and realizing the long cycle life of a potassium ion full battery. In particular, the specific ratio of the electrolyte and the specific combination of the functional fluorinated solvent and the potassium salt in example 2 can provide the P/C negative electrode material with the optimal electrochemical performance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, so they are regarded as main embodiments, but although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical method of the present invention without departing from the spirit and scope of the technical method of the present invention.
Claims (10)
1. The utility model provides a be applicable to local high concentration electrolyte of potassium ion battery which characterized in that: the electrolyte comprises a functional fluorinated solvent and a high-concentration ether electrolyte, wherein the high-concentration ether electrolyte consists of the ether solvent and sylvite, the sylvite concentration is 3-6 mol/L, and the volume ratio of the functional fluorinated solvent to the high-concentration ether electrolyte is 2-1.
2. The electrolyte of claim 1, wherein: <xnotran> 1,1,2,2- -2,2,3,3- , (2,2,2- ) , ( ) , (2,2,2- ) ,1H,1H,5H- 1,1,2,2- ,1- (2,2,2- ) -1,1,2,2- ,1,1,2,2- -2,2,2- , -1,1,1,3,3,3- ; </xnotran>
The ether solvent is one or more selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and 1, 3-dioxolane.
3. The electrolyte of claim 1, wherein: the potassium salt is one or more of potassium bis (fluorosulfonyl) imide, potassium bis (trifluoromethanesulfonyl) imide, potassium hexafluorophosphate, potassium perchlorate and potassium trifluoromethanesulfonate.
4. A method for preparing the local high-concentration electrolyte for the potassium ion battery according to any one of claims 1 to 3, characterized in that: dissolving potassium salt with a certain concentration in an ether solvent, fully stirring for a plurality of hours to prepare high-concentration ether electrolyte, then adding a functional fluorinated solvent into the high-concentration ether electrolyte according to a certain volume percentage, and fully stirring for a plurality of hours to prepare local high-concentration electrolyte.
5. The method according to claim 4, wherein: the stirring time of the high-concentration ether electrolyte is 24-72 hours, the stirring time of the local high-concentration electrolyte is 48-96 hours, and the stirring speed is 400-800 rpm.
6. A lithium-ion half-cell, characterized by: the battery comprises a P/C composite electrode, a composite diaphragm, a potassium metal negative electrode and the local high-concentration electrolyte of any one of claims 1 to 4.
7. A potassium ion full cell is characterized in that: the battery comprises a pre-potassized P/C composite negative electrode, a composite diaphragm, a pre-potassized 3,4,9, 10-perylene tetracarboxylic dianhydride positive electrode and the local high-concentration electrolyte as claimed in any one of claims 1 to 3.
8. The potassium ion full cell according to claim 7, wherein: the 3,4,9, 10-perylenetetracarboxylic dianhydride positive electrode consists of 60-80 wt.% of purified 3,4,9, 10-perylenetetracarboxylic dianhydride positive electrode material, 10-20 wt.% of acetylene black and 10-20 wt.% of polyvinylidene fluoride, and the components are firstly dissolved in a certain amount of N-methylpyrrolidone, then evenly coated on an aluminum foil, and subjected to vacuum driving at 70-100 ℃ for 12-36 hours to prepare the 3,4,9, 10-perylenetetracarboxylic dianhydride positive electrode.
9. The potassium ion full cell according to claim 7, wherein: the mass ratio of the active substances of the P/C negative electrode to the 3,4,9, 10-perylene tetracarboxylic dianhydride positive electrode is (1).
10. The potassium ion full cell according to claim 7, wherein: the pre-potassification process comprises the steps of pre-activating a P/C electrode and a 3,4,9, 10-perylene tetracarboxylic dianhydride electrode in a potassium ion half-cell for 3-5 times, and then discharging the electrodes to realize pre-potassification, wherein the pre-activation current densities of the P/C electrode and the 3,4,9, 10-perylene tetracarboxylic dianhydride electrode are 100-400 mA g -1 And 25-100 mA g -1 。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116072973A (en) * | 2023-03-06 | 2023-05-05 | 河北工业大学 | High-voltage potassium ion battery ether electrolyte and application thereof |
| CN116799312A (en) * | 2023-08-23 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | Secondary battery, electrolyte and electricity using device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116072973A (en) * | 2023-03-06 | 2023-05-05 | 河北工业大学 | High-voltage potassium ion battery ether electrolyte and application thereof |
| CN116072973B (en) * | 2023-03-06 | 2023-06-09 | 河北工业大学 | High-voltage potassium ion battery ether electrolyte and application thereof |
| CN116799312A (en) * | 2023-08-23 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | Secondary battery, electrolyte and electricity using device |
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