CN108172897B - Solid electrolyte, preparation method thereof and all-solid-state battery - Google Patents
Solid electrolyte, preparation method thereof and all-solid-state battery Download PDFInfo
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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
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a solid electrolyte, belonging to the field of batteries. The invention also discloses a preparation method of the solid electrolyte, which comprises the steps of adopting a molecular imprinting technology to take a polymer monomer and lithium salt as functional monomers, taking conductive particles as template molecules, adding an initiator and a cross-linking agent, dissolving in a solvent for cross-linking polymerization to form a polymer network structure wrapped with the lithium salt and the conductive particles, then washing away the conductive particles in the polymer network structure by using an eluent, and removing the solvent to form the solid electrolyte with a pore canal having a specific identification function on the conductive particles. Also discloses an all-solid-state battery comprising the positive pole piece, the negative pole piece, the aluminum plastic film and the solid electrolyte. The solid electrolyte has high ionic conductivity, strong compatibility with positive and negative electrode interfaces and small interface impedance, and the electrical property of the all-solid battery prepared by using the solid electrolyte is greatly improved.
Description
Technical Field
The invention belongs to the field of batteries, and relates to a solid electrolyte, a preparation method of the solid electrolyte, and an all-solid-state battery comprising the solid electrolyte.
Background
In recent years, with the rapid development of industries such as telecommunications and electric vehicles, rechargeable batteries for power and energy storage have also been rapidly growing. The increasing global environmental requirements and the development of new vehicles such as electric vehicles will drive the rapid development of battery industries such as lithium ion batteries, lithium sulfur batteries, and lithium air batteries. However, the rechargeable battery has certain safety problems in practical application, mainly because the organic electrolyte is easy to volatilize and leak, and is easy to induce safety accidents such as fire and explosion. The solid electrolyte is used as an ion conductor to realize the transfer of lithium ions between the active substances of the positive electrode and the negative electrode, and can be used as a diaphragm to separate the positive electrode and the negative electrode to prevent internal short circuit, thereby greatly improving the safety performance of the storage battery. However, the solid electrolyte has the characteristics of poor compatibility with an electrode interface, large interface resistance, low ionic conductivity and the like, and research progress of the solid battery is limited. Therefore, research and development of a solid electrolyte with high compatibility with an electrode interface and high performance has become a key point in the development of rechargeable batteries.
Disclosure of Invention
Technical problem to be solved
In order to solve the above problems in the prior art, an object of the present invention is to provide a solid electrolyte with high ionic conductivity, high compatibility with positive and negative electrode interfaces, reduced interface impedance, and improved electrical performance of a battery.
The second purpose of the invention is to provide a preparation method of the solid electrolyte.
It is a further object of the present invention to provide an all-solid battery using the above solid electrolyte.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
the present invention provides a solid electrolyte having a pore channel having a specific recognition function for conductive particles.
According to the invention, the particle size of the conductive particles is 5-40nm, and the pore diameter of the pore channel is 5-40 nm.
According to the invention, the conductive particles are one or more of carbon nanotubes, conductive graphite, conductive carbon black and Ketjen black.
Meanwhile, the invention provides a preparation method of the solid electrolyte, the solid electrolyte adopts a molecular imprinting technology, takes a polymer monomer and lithium salt as functional monomers, takes conductive particles as template molecules, adds an initiator and a cross-linking agent, dissolves in a solvent for cross-linking polymerization to form a polymer network structure wrapped with the lithium salt and the conductive particles, then utilizes an eluent to wash away the conductive particles in the polymer network structure, and removes the solvent to form the solid electrolyte with a pore canal having a specific recognition function for the conductive particles.
According to the invention, the molar ratio of the template molecule, the functional monomer and the cross-linking agent is 1-5:20-100:4-30, wherein the molar ratio of the polymer monomer in the functional monomer to lithium in the lithium salt is 6-8: 1.
According to the invention, the conductive particles are one or more of carbon nanotubes, conductive graphite, conductive carbon black and Ketjen black;
the particle size of the conductive particles is 5-40nm, and the pore diameter of the pore channel is 5-40 nm.
According to the invention, the eluent is one or more of chloroform, 1, 2-dichlorobenzene, methylnaphthalene and 1-bromo-2-methylnaphthalene.
According to the invention, the initiator is azobisisobutyronitrile and/or azobisisoheptonitrile, and the mass of the initiator accounts for 0.6-1.2% of the total weight of the solute.
According to the invention, the cross-linking agent is selected from one or more of ethylene glycol dimethacrylate, N, N '-methylenebisacrylamide, N, N' -1, 4-phenylene bisacrylamide, pentaerythritol triacrylate and trimethoxypropane trimethacrylate.
The invention also provides an all-solid-state battery which comprises a positive pole piece, a negative pole piece, an aluminum plastic film and the solid electrolyte.
(III) advantageous effects
Compared with the prior art, the invention has the following advantages:
1. the solid electrolyte is polymerized by using a molecular imprinting technology, has a porous channel beneficial to ion shuttling, and greatly improves the ion conductivity of the all-solid electrolyte;
2. the surface of the solid electrolyte has a pore passage left after the conductive particles are eluted, so that selective embedding sites are provided for the conductive particles on the surfaces of the positive electrode and the negative electrode, the interface compatibility with the positive electrode and the negative electrode is improved, and the interface impedance is reduced;
3. the pore channel left after the conductive particles on the solid electrolyte are eluted is beneficial to the shuttle of ions, and the micro short circuit of the battery caused by the perforation of the electrolyte membrane can not be caused.
4. The solid electrolyte can be applied to storage batteries such as lithium ion batteries, lithium sulfur batteries, lithium air batteries and the like, and can solve the problem of battery electrical property reduction caused by low solid electrolyte conductivity, poor compatibility between the solid electrolyte and an electrode interface and large interface resistance of the existing all-solid batteries.
Drawings
FIG. 1 is a schematic diagram of a solid-state electrolyte in which CNTs are washed away using an eluent leaving ion channels according to an embodiment of the present invention;
fig. 2 is a schematic view of the assembled positive and negative electrodes and solid electrolyte fabricated in the embodiment of the present invention, in which a is a partially enlarged view.
In the figure:
1. a solid electrolyte; 2. conductive particles; 3. a duct; 4. a positive electrode active material; 5. and a negative electrode active material.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The present embodiment proposes a solid electrolyte 1 having pores 3 having a specific recognition function for conductive particles 2. The pore channel 3 can facilitate the shuttling of ions, greatly improve the ionic conductivity of the solid electrolyte 1, avoid the micro short circuit of the battery caused by the perforation of an electrolyte membrane, provide selective embedding sites for the conductive particles 2 on the surfaces of the positive and negative electrodes, increase the interface compatibility with the positive and negative electrode plates and reduce the interface impedance, thereby solving the problems of the existing solid battery that the electrical property of the battery is reduced due to the low conductivity of the solid electrolyte 1, the poor compatibility of the solid electrolyte 1 and the electrode interface and the large interface impedance.
The solid electrolyte 1 of the embodiment can be applied to storage batteries such as lithium ion batteries, lithium sulfur batteries, lithium air batteries and the like, a molecular imprinting technology is adopted, a polymer monomer and a lithium salt are used as functional monomers, conductive particles 2 are used as template molecules, an initiator and a cross-linking agent are added and dissolved in a solvent, the mixture is stirred and mixed uniformly at the rotating speed of 800-2000r/min, the mixture is heated to 50-100 ℃ (preferably 80 ℃) for cross-linking polymerization to form a polymer network structure wrapped with the lithium salt and the conductive particles 2, then an eluant is used for washing away the conductive particles 2 in the polymer network structure, the solvent is removed through vacuum drying at 50-70 ℃ to form the solid electrolyte with a pore 3 having a specific identification function on the conductive particles 2, and the thickness of the prepared solid electrolyte 1 is 80-100 mu m. In order to improve the preparation efficiency and reduce the cost, the stirring speed is preferably 1000-1500r/min, and the optimal value is 1200 r/min; the heating temperature is preferably 60-85 ℃, and the optimal value is 80 ℃; the optimal optimized value of the vacuum drying temperature is 60 ℃; thus, the thickness of the prepared solid electrolyte 1 was kept in the range of 85 to 95 μm.
The molecular imprinting technology is a process for transferring various biological macromolecules from gel to a fixed matrix, and the basic principle is as follows: when the template molecule (the imprinting molecule) contacts with the monomer of the polymer, multiple sites are formed, which are memorized by the polymerization process, and when the template molecule is removed, a cavity with multiple sites matching the spatial configuration of the template molecule is formed in the polymer, which cavity will have selective recognition properties for the template molecule and the like.
The molecular imprinting technology has the following characteristics: 1. the prearrangement is that it can prepare different imprinted polymers MIPs according to different purposes to meet different requirements. 2. The identification, namely the imprinted polymer MIPS is customized according to the template molecule, and can specifically identify the imprinted molecule. 3. The utility is that it can be compared with natural biological molecule recognition system such as enzyme and substrate, antigen and antibody, receptor and hormone, but because it is prepared by chemical synthesis, it has the ability of resisting adverse environment which natural molecule recognition system does not possess, thus showing high stability and long service life.
In the present embodiment, the conductive particles 2 form multiple action points when they are contacted with the polymer monomer and the lithium salt, and a cross-linking polymerization reaction occurs under the action of the cross-linking agent and the initiator, and these multiple action points are memorized during the polymerization process, and after the conductive particles 2 are eluted by the eluent, cavities having multiple action points matching the spatial configuration of the conductive particles 2 are formed in the polymer, and such cavities have selective recognition properties for the conductive particles 2 and the like.
In the present embodiment, the polymer monomer mainly plays a supporting role in the electrolyte membrane. The polymer monomer is one or more of ethylene oxide, acrylonitrile, vinylidene fluoride, methyl methacrylate, propylene oxide and vinylidene chloride. After being mixed with an initiator and a cross-linking agent, the polymer monomers are heated to initiate polymerization reaction, and a corresponding polymer network structure is formed.
The lithium salt mainly plays a role in lithium ion migration and conduction in an electrolytic reaction system. The lithium salt is selected from one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethanesulfonyl imide, lithium oxalyldifluoroborate, lithium bis (pentafluoroethylsulfonyl) imide and lithium bis (oxalato) borate.
The conductive particles 2 are selected from one or more of Carbon Nanotubes (CNT), conductive graphite, conductive carbon black and Ketjen black. For example, one or more of conductive graphite SP-Li, conductive carbon black KS6, and ketjen black ECP, and any of the conductive particles described above may be selected as necessary.
The carbon nano tube has the general diameter of about 5nm and the length of 10-20 mu m, not only can serve as a 'wire' in a conductive network, but also has an electric double layer effect, exerts the high rate characteristic of the super capacitor, has good heat-conducting property, is beneficial to heat dissipation during charging and discharging of the battery, reduces polarization of the battery, improves the high and low temperature performance of the battery, and prolongs the service life of the battery.
The conductive graphite SP-Li has small particle size, is almost the same as conductive carbon black, but has moderate specific surface area, particularly exists in a battery in a branched form, is very beneficial to forming a conductive network, and has the defect of difficult dispersion.
The conductive carbon black KS6 is used as a conductive additive in a lithium ion electrode, the defect of the conductive carbon black is overcome, the conductive carbon black KS6 has small particle size, large specific surface area and good conductivity, and can play a role in absorbing and retaining liquid in a battery, and the defects of high price and difficult dispersion are overcome.
Ketjen black ECP is a carbon black produced by a very original special production process. Compared with the common conductive carbon black, the ketjen black ECP has a unique branched-chain form, and the form has the advantages that the conductive contacts of the conductor are more, the branched chains form more conductive paths, and therefore, the extremely high conductivity can be achieved only by a small amount of addition (other carbon blacks are mostly spherical or flaky, so that the required electrical property can be achieved by a high amount of addition). Because of the ultrahigh conductivity of the Ketjen black ECP, the usage amount of the Ketjen black ECP is less than that of other conductive carbon blacks, more active substances can be filled, the current density and the battery capacity of the battery are greatly improved, the service life of the battery can be prolonged, the Ketjen black ECP is particularly suitable for high-end lithium batteries, can also be used for nickel-hydrogen batteries, dry batteries and other types of batteries to improve the quality and the durability of products, and has good application effects in super capacitors and a plurality of conductive and shielding materials. Further, ketjen black ECP has another characteristic advantage that the resistance of the battery does not increase due to the change in volume during the charge and discharge processes because the branched form of ketjen black ECP has sufficient contact with the active material and does not lose contact due to the change in gap.
When the conductive particles 2 having a particle diameter of 5 to 40nm are selected, the surface of the solid electrolyte 1 finally formed has cell channels 3 having a specific function of identifying the conductive particles 2 having a particle diameter of 5 to 40 nm. When the particle diameter of the conductive particles 2 is ground to 10-30nm, the particle diameter of the pore channels 3 which are formed on the surface of the prepared solid electrolyte 1 and have the function of identifying the solid electrolyte is correspondingly controlled to 10-30 nm.
In this embodiment, the mass of the initiator is 0.6 to 1.2% of the total weight of the solute, and the amount is very small, and is preferably 0.8 to 1.1% for cost reduction. The compound which is easily decomposed into free radicals (primary free radicals) when heated can be used for initiating the free radical polymerization and copolymerization of alkene and diene monomers and can also be used for crosslinking curing and high molecular crosslinking reaction of unsaturated polyester.
The initiator is azodiisobutyronitrile and/or azodiisoheptonitrile which are low-activity initiators. The azodiisobutyronitrile is uniformly decomposed at the use temperature of 50-65 ℃, only forms a free radical, has no other side reaction, is relatively stable and can be safely stored in a pure state, but is also rapidly decomposed at the temperature of 80-90 ℃, and the azodiisobutyronitrile has the defects of low decomposition rate, and the formed isobutyronitrile free radical lacks dehydrogenation capability, so that the azodiisobutyronitrile cannot be used as an initiator for graft polymerization. The azodiisoheptonitrile has high activity and high initiation efficiency, and may be used to replace azodiisobutyronitrile, preferably azodiisoheptonitrile. The Azodiisobutyronitrile (AIBME) has moderate initiation activity, easy control of polymerization reaction, no residue in the polymerization process, high product conversion rate and harmless decomposition products, so that the azodiisobutyronitrile is an optimal substitute for azodiisobutyronitrile.
The cross-linking agent is one of important factors for successfully preparing the molecularly imprinted membrane, and can improve the cross-linking degree of the molecularly imprinted polymer, so that a host-guest complex formed by the imprinted molecules and the functional monomer can keep a better shape in the polymer to form a memorized cavity structure. However, it is clarified that if the degree of crosslinking of the imprinted polymer is too high, the elution and recovery of the imprinted molecules become difficult, and particularly for some expensive imprinted molecules, a great loss is caused; meanwhile, the high crosslinking degree deteriorates the accessibility of the imprinting sites and reduces the mass transfer rate, so that the practical application of the molecular imprinting technology is limited, and therefore, the selection of the type and the dosage of the crosslinking agent is the technical key of the molecular imprinting method membrane preparation.
In this embodiment, the crosslinking agent is one or more selected from ethylene glycol dimethacrylate, N, N '-methylenebisacrylamide, N, N' -1, 4-phenylenediacrylamide, pentaerythritol triacrylate, and trimethoxypropane trimethacrylate.
Ethylene glycol dimethacrylate (EDMA) is inexpensive, easy to purify, and stable in the properties of the prepared molecularly imprinted polymer, and therefore, it is preferable to select it as the crosslinking agent of the present embodiment. To prepare a highly crosslinked molecularly imprinted polymer to form well-ordered memory cavities, the molar ratio of functional monomer to EDMA is generally maintained at a level of 1: 5. In addition, N, N '-methylenebisacrylamide, N, N' -1, 4-phenylenediacrylamide, trimethoxypropanetrimethacrylate, 3, 5-bisacrylamidobenzoic acid, divinylbenzene, pentaerythritol triacrylate and the like are also customary crosslinking agents.
The ratio of the template molecules to the functional monomers has great influence on the generation of recognition holes in the molecularly imprinted membrane. The functional monomers and the ratio of the functional monomers to the template molecules are properly selected according to the types of the functional groups of the template molecules and the properties of the solvent system in the preparation process of the molecularly imprinted membrane. In addition, the ratio of the functional monomer and the cross-linking agent has a great influence on the performance of the blotting membrane. When the concentration of the cross-linking agent is low, the membrane liquid cannot reach enough cross-linking degree, the stable configuration of a cavity cannot be maintained, and the due recognition capability cannot be shown, but the unit volume of the membrane liquid contains a reduced number of functional monomers due to too high concentration of the cross-linking agent, so that the membrane recognition efficiency is influenced. Through experimental optimization, the molar ratio of the template molecules, the functional monomers (the mixture of the polymer monomers and the lithium salt) and the cross-linking agent is 1-5:20-100:4-30, wherein the molar ratio of the polymer monomers in the functional monomers to the lithium in the lithium salt is 6-8: 1. In order to reduce the cost, improve the preparation efficiency and obtain the electrolyte with good electrical property, the mol ratio of the template molecule, the functional monomer and the cross-linking agent is preferably 2-4:30-76:10-25, and the mol ratio of the polymer monomer in the functional monomer to the lithium in the lithium salt is preferably 6.8-7.8: 1.
The solvent is selected from one of propylene carbonate, dimethyl propionamide, acetonitrile and gamma-butyrolactone, and the polarity of the solvents is high, so that the lithium salt can be dissolved sufficiently, and high conductivity is obtained. The solvent may be added in an excessive amount to sufficiently dissolve the lithium salt, and the specific amount may be appropriately added according to the amount of the selected lithium salt.
In the present embodiment, the eluent is selected from one or more of chloroform, 1, 2-dichlorobenzene, methylnaphthalene, and 1-bromo-2-methylnaphthalene, and of course, other reagents capable of dissolving the conductive particles 2, such as butanol and ethylene glycol, may be selected, and after the conductive particles 2 are washed away, holes having multiple action points are formed in accordance with the spatial configuration of the conductive particles 2 used, so as to selectively identify such conductive particles 2 and the like. The added eluent needs to be excessive, so that the conductive particles 2 can be sufficiently dissolved, and the conductive particles 2 are eluted from the polymer network structure, thereby forming a pore channel structure.
A specific embodiment is now provided:
the method comprises the steps of taking a polymer monomer EO and a lithium salt LiTFSI as functional monomers, taking CNT as a template molecule, adding an initiator azobisisobutyronitrile and a cross-linking agent EDMA, dissolving in a solvent acetonitrile for cross-linking polymerization, and washing away the CNT by using chloroform as an eluent to form a PEO-based solid electrolyte A with the thickness of 90 mu m, wherein the PEO-based solid electrolyte A has a pore 3 (shown in figure 1) which has a specific recognition function on the CNT and has the pore diameter of 8 nm.
The specific preparation process of the PEO-based solid electrolyte a is as follows:
adding a functional monomer EO and lithium salt lithium bistrifluoromethylsulfonyl imide (LiTFSI), a template molecule CNT and a cross-linking agent ethylene glycol dimethacrylate into solvent acetonitrile according to a molar ratio of CNT to PEO to LiTFSI to ethylene glycol dimethacrylate to be 3:35:5:20, mixing, adding an initiator azobisisobutyronitrile with the mass accounting for 1% of the total mass of the PEO, the LiTFSI, the CNT and the ethylene glycol dimethacrylate, stirring and mixing uniformly at a stirring speed of 1200r/min, heating the mixture to 80 ℃ to perform cross-linking polymerization to form a PEO-based solid electrolyte which wraps the lithium salt and the CNT and has a polymer network structure, washing the CNT in the PEO-based polymer network structure by using excessive eluent chloroform, and performing vacuum drying at 60 ℃ to remove the acetonitrile to form the PEO-based solid electrolyte A with a specific recognition function pore path for the CNT.
In addition, the embodiment also provides an all-solid-state battery, which comprises the PEO-based solid electrolyte a, the positive electrode sheet B, the negative electrode sheet C and the aluminum plastic film D. The preparation method of the all-solid-state battery comprises the following steps:
B. positive pole piece: the positive active material 4 is one or more of Lithium Cobaltate (LCO), lithium nickel cobalt manganese oxide (NCM), lithium Nickel Cobalt Aluminate (NCA), lithium iron phosphate (LFP), Lithium Manganese Oxide (LMO), lithium-rich manganese base, oxygen and sulfur, the preferred embodiment is NCM, and the mass percentage of the positive active material 4 is 70-99.9%; the conductive agent is one or more of CNT, graphene, conductive graphite, conductive carbon black, Ketjen black ECP and carbon fiber (VGCF), and the mass percentage of the conductive agent is 0.1-15%; the binder is one or more of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), fluorinated rubber and polyurethane, and the binder accounts for 0.1-15%.
C. Negative pole piece: the negative active material 5 is one or more of artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, soft carbon, Lithium Titanate (LTO), silicon-based negative electrodes, tin-based negative electrodes, graphene, metal lithium and zinc alloy, the preferred embodiment is the artificial graphite, and the mass percentage of the negative active material 5 is 70-99.9%; the conductive agent is one or more of CNT, graphene, conductive graphite, conductive carbon black, Ketjen black ECP and VGCF, and the mass percentage of the conductive agent is 0.1-15%; the binder is one or more of PVDF, PVA, CMC, SBR, fluorinated rubber and polyurethane, and accounts for 0.1-15%.
D. Aluminum plastic film: mainly comprises an outer nylon layer, a middle aluminum layer and an inner PP layer.
And preparing the components A-D into finished product battery cores according to corresponding battery processes, and preparing the rechargeable storage battery after formation, standing and capacity grading.
As shown in fig. 2, when the positive electrode, the negative electrode and the all-solid-state electrolyte are assembled into an electrode assembly, the PEO-based solid-state electrolyte a has the pore channels 3 left after the elution of the CNTs, so as to provide selective embedding sites for the CNTs on the surfaces of the positive and negative electrodes, and increase the interface compatibility with the positive and negative electrode sheets, thereby reducing the interface impedance and improving the electrical performance of the battery.
It should be understood that the above description of specific embodiments of the present invention is only for the purpose of illustrating the technical lines and features of the present invention, and is intended to enable those skilled in the art to understand the contents of the present invention and to implement the present invention, but the present invention is not limited to the above specific embodiments. It is intended that all such changes and modifications as fall within the scope of the appended claims be embraced therein.
Claims (7)
1. A method of preparing a solid electrolyte, characterized by:
the solid electrolyte takes a polymer monomer and a lithium salt as functional monomers, conductive particles (2) as template molecules, an initiator and a cross-linking agent are added and dissolved in a solvent for cross-linking polymerization to form a polymer network structure wrapped with the lithium salt and the conductive particles (2), then an eluant is used for washing away the conductive particles (2) in the polymer network structure, and the solid electrolyte with pore channels (3) having specific identification functions on the conductive particles (2) is formed after the solvent is removed.
2. The method for producing a solid electrolyte according to claim 1, characterized in that:
the molar ratio of the template molecules to the functional monomers to the cross-linking agent is 1-5:20-100:4-30, wherein the molar ratio of the polymer monomers in the functional monomers to the lithium in the lithium salt is 6-8: 1.
3. The method for producing a solid electrolyte according to claim 1, characterized in that:
the conductive particles (2) are one or more of carbon nanotubes, conductive graphite, conductive carbon black and Ketjen black;
the particle size of the conductive particles (2) is 5-40nm, and the pore diameter of the pore channel (3) is 5-40 nm.
4. The method for producing a solid electrolyte according to claim 1, characterized in that:
the eluent is one or more of chloroform, 1, 2-dichlorobenzene, methylnaphthalene and 1-bromo-2-methylnaphthalene.
5. The method for producing a solid electrolyte according to claim 1, characterized in that:
the initiator is azobisisobutyronitrile and/or azobisisoheptonitrile, and the mass of the initiator accounts for 0.6-1.2% of the total weight of the solute.
6. The method for producing a solid electrolyte according to claim 1, characterized in that:
the cross-linking agent is one or more selected from ethylene glycol dimethacrylate, N, N '-methylene diacrylamine, N, N' -1, 4-phenylene diacrylamide, pentaerythritol triacrylate and trimethoxypropane trimethacrylate.
7. The utility model provides an all-solid-state battery, includes positive pole piece, negative pole piece and plastic-aluminum membrane, its characterized in that: further comprising a solid electrolyte prepared by the preparation method according to any one of claims 1 to 6.
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| PCT/CN2018/119157 WO2019128643A1 (en) | 2017-12-29 | 2018-12-04 | Solid electrolyte and preparation method therefor, and all-solid battery |
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| CN109950618B (en) * | 2019-03-26 | 2021-02-02 | 西安交通大学 | Solvated composite solid electrolyte and preparation method and application thereof |
| CN112382793B (en) * | 2019-07-29 | 2023-06-27 | 通用汽车环球科技运作有限责任公司 | Sulfide impregnated solid state battery |
| CN110492170A (en) * | 2019-08-30 | 2019-11-22 | 电子科技大学 | A kind of high ionic conductivity composite solid electrolyte and preparation method thereof |
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