CN105098232A - All-solid-state polymer electrolyte and preparation method and application thereof - Google Patents

Abstract

The invention provides all-solid-state polymer electrolyte. The electrolyte is a mixture of a fluorine-containing sulfonyl imide ion polymer and an ether oxo-containing polymer, wherein the mixture contains an -SO2N<->SO2- superacid polyanion structure; relatively high ionic conductivity and ion transference number can be obtained without adding a solvent; and meanwhile, an electrochemical window which is greater than 6V is obtained. An all-solid-state lithium secondary battery employing an electrolyte membrane can be charged and discharged at above 60 DEG C. Therefore, the all-solid-state polymer electrolyte has a wide application prospect in the fields such as a lithium-sulfur battery system, a high-voltage lithium battery system, a super capacitor and a high-temperature fuel cell.

Description

A kind of all-solid polymer electrolyte, its preparation method and application

technical field

The invention relates to the technical field of polymer electrolytes, in particular to an all-solid polymer electrolyte, its preparation method and application.

Background technique

Since the beginning of the 21st century, industry has developed rapidly, science and technology have been advancing day by day, and human demand for energy is increasing day by day. However, the excessive consumption of non-renewable energy is not conducive to the maintenance of ecological balance and sustainable development. Finding an environmentally friendly and effective new energy system is an urgent problem to be solved. As a result, new energy systems such as lithium-ion batteries, supercapacitors, and fuel cells have become research hotspots around the world.

Electrolyte material is the carrier of ion transmission in the new energy system, and it is also the key material for the normal operation of the new energy system. Taking lithium batteries as an example, the electrolyte separator is the carrier for lithium ions to be transmitted between the positive and negative electrodes of the battery, which has an important impact on the capacity, cycle performance, safety performance, working temperature range, and potential range of the battery. The research on polymer electrolytes in lithium-ion batteries began in the 1970s, when Wright discovered an ion-conductive polyethylene oxide-electrolyte salt system. Subsequently, Armand proposed the concept of solid-state electrolytes, and people began to study polymer electrolytes.

Compared with liquid electrolytes, polymer electrolytes can reduce the use of organic solvents, prevent liquid leakage, slow down the formation of lithium dendrites, and improve battery safety. Compared with gel polymer electrolytes that use a small amount of organic solvents, all-solid polymer electrolytes do not use liquid solvents, but only consist of polymers and lithium salts, which is equivalent to dissolving lithium salts in solid solvents such as polymers. This all-solid structure is less prone to internal short circuit and electrolyte leakage, and has high safety. On the other hand, the polymer structure can withstand the volume change of the electrode material during the charging and discharging process through the chain segment movement, improving the cycle performance. Furthermore, due to the easy processing of polymers, ultra-thin lithium batteries can be prepared by using all-solid electrolyte separators, and the shape plasticity is high.

In a common all-solid-state electrolyte system, such as polyethylene oxide-bistrifluorosulfonimide lithium (PEO-TFSI), the transfer of lithium ions is achieved through the segmental movement of the flexible polymer amorphous region, so in PEO Below the glass transition temperature (about 69°C), the movement of the chain segments is restricted, and the conductivity of the electrolyte system is low. On the other hand, the migratable anions in small-molecule lithium salts lead to a low lithium ion migration number. Furthermore, the electrochemical stability of this type of electrolyte separator is usually below 4.5V, which can only be used in common lithium battery systems such as lithium iron phosphate, lithium manganese oxide, and lithium cobalt oxide, and cannot be matched with high-voltage electrode materials to prepare high-voltage lithium batteries. The high-voltage lithium battery is an important direction for the development of lithium batteries.

Armand et al. published an article entitled "Single-ionBABtriblockcopolymershighlyefficientelectrolytesforlithium-metalbatteries" in the journal NatureMaterials, and prepared a triblock polymer electrolyte membrane with sulfonimide side groups of styrene and ethylene oxide. The conductivity of the membrane is 60 The temperature can reach 1.3×10 ^-5 S/cm, and the lithium ion migration number is 0.85. It was found by cyclic voltammetry that compared with the PEO-TFSI small molecule lithium salt system, the ionic polymer obtained by grafting sulfonimide groups onto the polymer main chain had higher electrochemical stability.

Contents of the invention

The invention provides an all-solid polymer electrolyte without adding solvent or plasticizer, which has the advantages of high electrical conductivity, lithium ion migration number close to 1, wide electrochemical window and the like.

The technical solution provided by the present invention is: an all-solid polymer electrolyte, which is a mixture of an ether-oxygen-containing polymer and a fluorine-containing sulfonimide lithium-ion polymer;

The ether-oxygen-containing polymer includes, but is not limited to, one or more of polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene oxide derivatives, polypropylene oxide derivatives, etc.;

The structural formula of described fluorine-containing sulfonylimide lithium ion polymer is as follows:

Wherein, R _f refers to -C _m F _{2m -or} -[CF ₂ CF ₂ ]OCF ₂ CF ₂ -, m is an integer from 1 to 40, including 1 and 40; the degree of polymerization n is an integer from 10 to 2000, including 10 and 2000.

Preferably, the degree of polymerization n is an integer ranging from 500 to 2000, including 500 and 2000.

Preferably, in the all-solid polymer electrolyte, the molar ratio of the etheroxy group (-CH ₂ O-) in the etheroxy-containing polymer to the fluorine-containing sulfonimide lithium-ion polymer is 4:1 ~50:1, more preferably 8:1~35:1, most preferably 20:1~30:1.

The preparation method of the all-solid polymer electrolyte material of the present invention can adopt the following steps:

Step 1: dissolving and mixing the etheroxy-containing polymer and the fluorine-containing sulfonimide lithium ion polymer in a solvent to obtain a mixed solution;

Step 2: In a dry environment, the mixed solution described in step 1 is prepared by a solution casting method to prepare a solid polymer electrolyte material.

In the step 1, the preparation of the mixed solution may be: dissolving the etheroxy-containing polymer and the fluorine-containing sulfonimide lithium ion polymer in a solvent respectively, and then mixing to obtain a mixed solution; it may also be: The dry ether oxygen-containing polymer and the fluorine-containing sulfonyl imide lithium ion polymer are first mixed, and then dissolved with a solvent to obtain a mixed solution.

In step 1, the solvent includes but is not limited to one of acetonitrile, ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, triethyl phosphate, etc. or a mixture of two or more.

In the step 2, the moisture content in the preferred dry environment is less than 150ppm.

In summary, the all-solid-state polymer electrolyte provided by the present invention contains fluorine-containing sulfonimide lithium ion polymer, and the main chain of the polymer is -SO ₂ N ^- Li ⁺ SO ₂ -structure, in which fluorine sulfonyl The amine group is a super-strong acid group, and the lone pair of electrons on the nitrogen atom is highly delocalized because it is connected with two strong electron-withdrawing perfluoroalkyl groups, which greatly weakens the electrostatic force between anion and cation, so that the fluorine-containing Lithium ions (Li ⁺ ) of sulfonimide lithium ion polymers have lower dissociation energy and lattice energy, and higher lithium ion conductance; at the same time, the structure of polyanions makes their anions fixed, and the number of cation ion migration is 1. That is, compared with the prior art, the present invention introduces fluorine-containing sulfonimide lithium ion polymer into the polymer electrolyte system as a polymer lithium salt, so that the all-solid polymer electrolyte system has the following advantages:

(1) It is a self-supporting electrolyte separator with excellent electrical conductivity and mechanical properties, and the ion conductivity can reach 10 ^-4 S/cm;

(2) Good thermal stability, no organic solvent added, and internal short circuit is not easy to occur, so when used in batteries, the safety performance of batteries can be improved;

(3) The electrochemical window is wide, and its electrochemical window is higher than 6V through cyclic voltammetry tests, so when used in lithium-ion battery systems, lithium-ion batteries with high voltage and high specific energy can be prepared;

(4) The cation transfer number is 1, therefore, when used in a battery, it is beneficial to reduce the cycle performance and lifespan of the battery caused by concentration polarization;

(5) It has excellent battery cycle performance. Experiments have confirmed that the all-solid lithium battery made with the all-solid polymer electrolyte of the present invention can cycle stably above 60°C;

And, experiments have confirmed that when the lithium salt in the all-solid polymer electrolyte is the polymer lithium salt of the fluorine-containing sulfonimide selected by the present invention, compared with the small-molecule lithium salt of the fluorine-containing sulfonimide, The all-solid-state electrolyte has high electrical conductivity, a lithium ion transfer number close to 1, a wide electrochemical window (its electrochemical window is higher than 6V), excellent battery cycle stability, and excellent discharge specific capacity. Therefore, the all-solid polymer electrolyte of the present invention has wider application prospects, for example, it can be applied to technical fields such as general-purpose lithium-ion batteries, high-voltage lithium batteries, supercapacitors, and high-temperature fuel cells.

When the all-solid polymer electrolyte of the present invention forms an all-solid-state lithium battery with the electrode and the negative electrode, the positive electrode is not particularly limited, and can be made of lithium cobaltate, lithium manganate, lithium nickel manganate and other compounds, or can be Sulfur-based positive electrode material; the negative electrode is not particularly limited, and can be made of graphite, metallic lithium, and the like. Discharge specific capacity under the same conditions.

Description of drawings

Fig. 1 is the conductivity curve of the all-solid electrolyte made in the embodiment of the present invention 1;

Fig. 2 is the charge-discharge curve of the all-solid-state lithium secondary battery prepared in Example 1 of the present invention;

Fig. 3 is a comparison chart of cyclic voltammetry curves of all solid electrolytes prepared in Example 1 and Comparative Example 1.

Detailed ways

The present invention will be further described in detail below with reference to the embodiments of the accompanying drawings. It should be noted that the following embodiments are intended to facilitate the understanding of the present invention, but do not limit it in any way.

Example 1:

In this embodiment, the all-solid polymer electrolyte is a mixture of polyethylene oxide (PEO) and fluorine-containing sulfonimide lithium ion polymer (PFSI), and the structural formula of the fluorine-containing sulfonimide lithium ion polymer is:

Wherein, the molar ratio of the ether oxygen bonds (-CH ₂ O-) in the polyethylene oxide to the lithium ions in the fluorine-containing sulfonimide lithium ion polymer is 25:1.

The preparation method of the above-mentioned all-solid polymer electrolyte is as follows:

Take 0.1 g of fluorine-containing sulfonylimide lithium ion polymer (PFSI) and add it to acetonitrile, stir for 5 hours to prepare a PFSI solution with a mass ratio of 10%; take 0.3 g of polyethylene oxide (PEO) and add it to acetonitrile, stir for 5 hours, Prepare a PEO solution with a mass ratio of 10%; mix the PFSI solution and the PEO solution, and stir magnetically for about 10 hours to obtain a mixed solution; in a desiccator, pour the mixed solution into a tetrafluoroethylene petri dish to form a film, and wait for the solvent to evaporate Finally, it was further dried in a vacuum oven at room temperature to obtain an all-solid polymer electrolyte, which was stored in a glove box for future use.

Figure 1 is a curve of the electrical conductivity of the all-solid polymer electrolyte prepared above as a function of temperature. It can be seen from Figure 1 that the conductivity of the all-solid polymer electrolyte reaches 10 ^-4 S/cm at 80°C, and when the temperature is further increased to 100°C, the conductivity can reach 10 ^-3 S/cm.

The positive electrode is made of lithium iron phosphate, the negative electrode is made of lithium sheet, and the above-mentioned all-solid polymer electrolyte is assembled in a glove box to obtain an all-solid lithium secondary battery. The test shows that when the temperature is higher than 60°C, the all-solid lithium secondary battery can still charge and discharge stably, and the charge and discharge curve is stable when the rate is 0.1C at 70°C, as shown in Figure 2, the discharge platform voltage is 3.4V, The capacity reaches 149mAh/g. At 0.2C rate and 80℃, the specific discharge capacity can be maintained at 140mAh/g. This result is higher than the PEO-LiCF ₃ SO ₃ electrolyte reported in the article entitled "Enhanced Lithium Battery with Polyethylene Oxide-Based Electrolyte Containing Silane-Al ₂ O ₃ ceramic Filler" published on ChemSusChem in 2013 by Zewde Berhanu et al. The discharge capacity at 100mAh/g is even higher than 30mAh/g.

Comparative Example 1:

This example is a comparative example of Example 1 above.

In this embodiment, the all-solid-state electrolyte diaphragm is a mixture formed by mixing polyethylene oxide (PEO) and bistrifluorosulfonimide lithium (TFSILi) small-molecule lithium salt, wherein the ether oxygen bond (-CH The molar ratio of ₂ O-) to the lithium ions in the small molecule lithium salt is 25:1.

The preparation method of the above-mentioned all-solid polymer electrolyte is basically the same as that of Example 1, except that the small-molecule lithium salt of bistrifluorosulfonylimide lithium (TFSILi) is used instead of the fluorine-containing sulfonylimide lithium ion polymer (PFSI) .

The all-solid polymer electrolytes in the above-mentioned Example 1 and Comparative Example 1 were assembled into experimental half-cells with stainless steel as the counter electrode and metal lithium as the reference electrode under the condition that the water content was 0.1 ppm. Cyclic voltammetry tests were performed at 70°C between 5V and 0-6V to characterize the decomposition voltage of the obtained all-solid polymer electrolyte relative to metal lithium.

Fig. 3 is a graph showing cyclic voltammetry test curves of all solid polymer electrolyte membranes prepared in Example 1 and Comparative Example 1. Wherein the solid line represents the electrolyte separator prepared with fluorine-containing sulfonimide lithium ion polymer (PFSI) and polyethylene oxide (PEO) in Example 1, and the dotted line represents the electrolyte separator prepared with polyethylene oxide (PEO) and double Electrolyte separator prepared from lithium trifluorosulfonyl imide (TFSILi) small molecule lithium salt. It can be seen from Figure 3 that for the small molecule lithium salt system, the separator is electrochemically unstable when the voltage reaches 4.5V; while for the polymer lithium salt system, the cyclic voltammetry curve can still remain stable when the voltage is increased to 6V. Oxidation peaks appear, electrochemical stability. It shows that the fluorine-containing sulfonylimide lithium ion polymer (PFSI) and polyethylene oxide (PEO) system electrolyte diaphragm has a wider range of voltage applications, and is more suitable for the use requirements of high-voltage systems.

Example 2:

In this example, the all-solid polymer electrolyte is basically the same as in Example 1, except that the ether oxygen bond (-CH ₂ O-) in the polyethylene oxide and the lithium in the fluorine-containing sulfonimide lithium ion polymer The molar ratio of ions is 30:1.

The preparation method of the solid polymer electrolyte in this example is basically the same as that of the example, except that the ether oxygen bond (-CH ₂ O-) in polyethylene oxide and the fluorine-containing sulfonimide lithium ion polymer The molar ratio of lithium ions is 30:1.

According to the AC impedance spectrum of the all-solid polymer electrolyte, the conductivity of the all-solid polymer electrolyte at 80° C. is 1.85×10 ⁻⁴ S/cm.

Same as Example 1, lithium iron phosphate was used to make the positive electrode, and lithium sheets were used to make the negative electrode, and assembled with the all-solid polymer electrolyte in this example in a glove box to obtain an all-solid lithium secondary battery. Tests show that the all-solid lithium secondary battery can be charged and discharged stably, the charge and discharge curve is stable at 70°C, and the discharge plateau voltage is about 3.4V.

According to the test method in Comparative Example 1, it is measured that it has an electrochemical window higher than 6V.

Example 3:

In this example, the all-solid polymer electrolyte is basically the same as in Example 1, except that the ether oxygen bond (-CH ₂ O-) in the polyethylene oxide and the lithium in the fluorine-containing sulfonimide lithium ion polymer The molar ratio of ions is 20:1.

The preparation method of the solid polymer electrolyte in this example is basically the same as that in the example, except that the ether oxygen bond (-CH ₂ O-) in polyethylene oxide and the fluorine-containing sulfonimide lithium ion polymer The molar ratio of lithium ions is 20:1.

According to the AC impedance spectrum of the all-solid polymer electrolyte, the conductivity of the all-solid polymer electrolyte at 80° C. is 7.5×10 ⁻⁵ S/cm.

Same as Example 1, lithium iron phosphate was used to make the positive electrode, and lithium sheets were used to make the negative electrode, and assembled with the all-solid polymer electrolyte in this example in a glove box to obtain an all-solid lithium secondary battery. Tests show that the all-solid lithium secondary battery can be charged and discharged stably, and the charge and discharge curve is stable at 70°C.

According to the test method in Comparative Example 1, it is measured that it has an electrochemical window higher than 6V.

Example 4:

In this example, the all-solid polymer electrolyte is basically the same as in Example 1, except that the ether oxygen bond (-CH ₂ O-) in polyethylene oxide and the lithium in the fluorine-containing sulfonimide lithium ion polymer The molar ratio of ions is 16:1.

The preparation method of the solid polymer electrolyte in this example is basically the same as that of the example, except that the ether oxygen bond (-CH ₂ O-) in polyethylene oxide and the fluorine-containing sulfonimide lithium ion polymer The molar ratio of lithium ions is 16:1.

According to the AC impedance spectrum of the all-solid polymer electrolyte, the conductivity of the all-solid polymer electrolyte at 80° C. is 1.3×10 ⁻⁴ S/cm.

Same as Example 1, lithium iron phosphate was used to make the positive electrode, and lithium sheets were used to make the negative electrode, and assembled with the all-solid polymer electrolyte in this example in a glove box to obtain an all-solid lithium secondary battery. Tests show that the all-solid-state lithium secondary battery can be charged and discharged stably.

According to the test method in Comparative Example 1, it is measured that it has an electrochemical window higher than 6V.

Example 5:

In this example, the all-solid polymer electrolyte is basically the same as in Example 1, except that the ether oxygen bond (-CH ₂ O-) in the polyethylene oxide and the lithium in the fluorine-containing sulfonimide lithium ion polymer The molar ratio of ions is 8:1.

The preparation method of the solid polymer electrolyte in this example is basically the same as that in the example, except that the ether oxygen bond (-CH ₂ O-) in polyethylene oxide and the fluorine-containing sulfonimide lithium ion polymer The molar ratio of lithium ions is 8:1.

According to the AC impedance spectrum of the all-solid polymer electrolyte, the conductivity of the all-solid polymer electrolyte at 80° C. is 1.5×10 ⁻⁵ S/cm.

Same as Example 1, lithium iron phosphate was used to make the positive electrode, and lithium sheets were used to make the negative electrode, and assembled with the all-solid polymer electrolyte in this example in a glove box to obtain an all-solid lithium secondary battery. Tests show that the all-solid-state lithium secondary battery can be charged and discharged stably.

According to the test method in Comparative Example 1, it is measured that it has an electrochemical window higher than 6V.

Embodiment 6:

In this embodiment, the all-solid polymer electrolyte is exactly the same as that in Embodiment 1.

The preparation method of the solid polymer electrolyte in this embodiment is as follows:

Mix 0.1g fluorine-containing sulfonylimide lithium ion polymer (PFSI) with 0.35g polyethylene oxide (PEO), dry in a vacuum oven at 100°C, and then dissolve in acetonitrile to form a 10% solution by mass. Stir for 15 hours, transfer to an inert gas operation box, and then pour the solution into a tetrafluoroethylene petri dish to form a film. After the solvent evaporates, it is further dried in a vacuum oven at room temperature to obtain an all-solid polymer electrolyte, which is stored in a glove box for future use.

It was determined that, as in Example 1, the all-solid polymer electrolyte prepared above had good electrical conductivity, reaching 10 ^-4 S/cm at 80°C and close to 10 ^-3 S/cm at 100°C.

Same as Example 1, the positive electrode was made of lithium iron phosphate, the negative electrode was made of lithium sheet, and assembled with the above-mentioned all-solid polymer electrolyte in a glove box to obtain an all-solid lithium secondary battery. Tests show that the all-solid lithium secondary battery can be charged and discharged stably.

According to the test method in Comparative Example 1, it is measured that it has an electrochemical window higher than 6V.

Embodiment 7:

In this embodiment, the all-solid polymer electrolyte is a mixture formed by mixing polypropylene oxide (PPO) with a fluorine-containing sulfonimide lithium ion polymer, and the structural formula of the fluorine-containing sulfonimide lithium ion polymer is:

Wherein, the molar ratio of the ether oxygen bonds (-CH ₂ O-) in the polyethylene oxide to the lithium ions in the fluorine-containing sulfonimide lithium ion polymer is 20:1.

The preparation method of the above-mentioned all-solid polymer electrolyte is as follows:

Take 0.1 g of fluorine-containing sulfonimide lithium ion polymer and add it to acetonitrile, stir for 5 hours to prepare a fluorine-containing sulfonyl imide lithium ion polymer solution with a mass ratio of 10%; take 0.35 g of polyoxypropylene (PPO) and add In acetonitrile, stir for 5 hours to prepare a PPO solution with a mass ratio of 10%; mix the fluorine-containing sulfonimide lithium ion polymer solution with the PPO solution, and magnetically stir for about 10 hours to obtain a mixed solution; in a desiccator, mix the The solution was poured into a tetrafluoroethylene petri dish to form a film, and after the solvent evaporated, it was further dried in a vacuum oven at room temperature to obtain an all-solid polymer electrolyte, which was stored in a glove box for future use.

Same as Example 1, the positive electrode was made of lithium iron phosphate, the negative electrode was made of lithium sheet, and assembled with the above-mentioned all-solid polymer electrolyte in a glove box to obtain an all-solid lithium secondary battery. Tests have shown that the all-solid lithium secondary battery can be charged and discharged stably.

According to the test method in Comparative Example 1, it is measured that it has an electrochemical window higher than 6V.

The embodiments described above have described the technical solutions of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the present invention. All done within the principle scope of the present invention Any modification, supplement or substitution in a similar manner shall be included within the protection scope of the present invention.

Claims (10)

1. An all-solid polymer electrolyte, characterized in that: the all-solid polymer electrolyte is a mixture of fluorine-containing sulfonimide lithium ion polymer and ether oxygen-containing polymer, and the fluorine-containing sulfonimide The structural formula of lithium ion polymer is as follows: Wherein, R _f refers to -C _m F _{2m -or} -[CF ₂ CF ₂ ]OCF ₂ CF ₂ -, m is an integer from 1 to 40, including 1 and 40; the degree of polymerization n is an integer from 10 to 2000, including 10 and 2000. 2. The all-solid polymer electrolyte according to claim 1, characterized in that: said degree of polymerization n is an integer ranging from 500 to 1500, including 500 and 1500. 3. The all-solid polymer electrolyte according to claim 1, characterized in that: said ether-oxygen-containing polymer is polyoxyethylene, polyoxypropylene, polyoxyethylene derivatives, polyoxypropylene derivatives One or a mixture of two or more. 4. The all-solid polymer electrolyte according to claim 1, characterized in that: in the all-solid polymer electrolyte, the ether oxygen group in the ether oxygen-containing polymer and the fluorine-containing sulfonimide lithium ion The molar ratio of the polymers is 4:1-50:1, preferably 8:1-35:1, more preferably 20:1-30:1. 5. The all-solid polymer electrolyte according to any one of claims 1 to 4, characterized in that its electrochemical window is higher than 6V. 6. The all-solid polymer electrolyte according to any one of claims 1 to 4, characterized in that: the all-solid-state lithium battery made of the all-solid polymer electrolyte can cycle stably above 60°C. 7. The method for preparing the all-solid polymer electrolyte according to any one of claims 1 to 4, characterized in that: comprising the steps of: Step 1: dissolving and mixing the etheroxy-containing polymer and the fluorine-containing sulfonimide lithium ion polymer in a solvent to obtain a mixed solution; Step 2: In a dry environment, the mixed solution described in step 1 is prepared by a solution casting method to prepare a solid polymer electrolyte. 8. The preparation method of the all-solid polymer electrolyte according to claim 7, characterized in that: in the step 1, the preparation of the mixed solution is: the ether oxygen-containing polymer and the fluorine-containing lithium sulfonimide The ionic polymers are respectively dissolved in a solvent, and then mixed to obtain a mixed solution; or: the dry ether-oxygen-containing polymer and the fluorine-containing sulfonimide lithium ion polymer are mixed first, and then dissolved in a solvent to obtain a mixed solution . 9. The preparation method of all solid polymer electrolyte according to claim 7, characterized in that: in the step 1, the solvent includes acetonitrile, ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, One or a mixture of two or more of N,N-dimethylformamide and triethyl phosphate. 10. Application of the all-solid-state polymer electrolyte according to any one of claims 1 to 4 in lithium-ion batteries, high-voltage lithium batteries, supercapacitors, and high-temperature fuel cells.