WO2019128643A1 - 固态电解质及其制备方法和全固态电池 - Google Patents

固态电解质及其制备方法和全固态电池 Download PDF

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WO2019128643A1
WO2019128643A1 PCT/CN2018/119157 CN2018119157W WO2019128643A1 WO 2019128643 A1 WO2019128643 A1 WO 2019128643A1 CN 2018119157 W CN2018119157 W CN 2018119157W WO 2019128643 A1 WO2019128643 A1 WO 2019128643A1
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solid electrolyte
conductive particles
lithium
conductive
preparation
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French (fr)
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范欢欢
娄忠良
孙敏敏
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Soundgroup Co Ltd
Soundon New Energy Technology Co Ltd
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Soundgroup Co Ltd
Soundon New Energy Technology Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of batteries, and in particular to a solid electrolyte and a preparation method thereof, and an all solid state battery including the solid electrolyte.
  • the rechargeable battery has certain safety problems, mainly because the organic electrolyte is prone to volatilization and leakage, and it is easy to induce fire, explosion and other safety accidents.
  • the all-solid-state battery made of solid electrolyte uses solid electrolyte as the ionic conductor to realize the transfer of lithium ions between the positive and negative active materials, and can be used as a separator to separate the positive and negative electrodes to prevent internal short circuit, which greatly improves the safety performance of the battery. .
  • Another object of the present invention is to provide a method for producing the above solid electrolyte.
  • a third object of the present invention is to provide an all solid state battery including the above solid electrolyte.
  • the main technical solutions adopted by the present invention include:
  • a solid electrolyte having a channel having a spatial configuration matching a conductive particle to specifically identify the conductive particle.
  • the pore size of the pores matches the particle size of the electrically conductive particles.
  • the pores have a pore diameter of 5 to 40 nm, and the conductive particles have a particle diameter of 5 to 40 nm.
  • the conductive particles are one or more selected from the group consisting of carbon nanotubes, conductive graphite, conductive carbon black, and ketjen black.
  • the solid electrolyte comprises: a lithium salt, and a polymer network structure encasing the lithium salt; wherein the pores are located in the polymer network structure.
  • the polymer monomer forming the polymer network structure is selected from one or more of the group consisting of ethylene oxide, acrylonitrile, vinylidene fluoride, methyl methacrylate, propylene oxide, and vinylidene chloride.
  • the molar ratio between the polymer monomer forming the polymer network structure and the lithium in the lithium salt is from 6 to 8:1.
  • a method for preparing a solid electrolyte using a molecular imprinting technique using a polymer monomer and a lithium salt as a functional monomer, a conductive particle as a template molecule, an initiator and crosslinking is provided.
  • the agent is dissolved in a solvent for cross-linking polymerization, and includes the following steps:
  • crosslinking polymerization is carried out by adding a functional monomer, a conductive particle, an initiator, and a crosslinking agent to a solvent, the functional monomer comprising a polymer monomer and a lithium salt to form a coating of the lithium salt and the conductive particle.
  • a functional monomer comprising a polymer monomer and a lithium salt to form a coating of the lithium salt and the conductive particle.
  • the molar ratio of the conductive particles, the functional monomer and the crosslinking agent is 1-5:20-100:4-30, wherein the molar ratio of the polymer monomer in the functional monomer to the lithium in the lithium salt The ratio is 6-8:1.
  • the polymer monomer is selected from one or more of ethylene oxide, acrylonitrile, vinylidene fluoride, methyl methacrylate, propylene oxide, and vinylidene chloride.
  • the conductive particles are one or more selected from the group consisting of carbon nanotubes, conductive graphite, conductive carbon black, and ketjen black.
  • the conductive particles have a particle diameter of 5 to 40 nm, and the pores have a pore diameter of 5 to 40 nm.
  • the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, lithium bisfluorosulfonimide, lithium trifluoromethylsulfonimide, lithium oxalate difluoroborate One or more of lithium bis(pentafluoroethylsulfonyl)imide and lithium dioxalate borate.
  • the eluent is selected from one or more of chloroform, 1,2-dichlorobenzene, methylnaphthalene, 1-bromo-2-methylnaphthalene, butanol, ethylene glycol.
  • the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile and dimethyl azobisisobutyrate, the initiator being in the mass of the polymer monomer 0.6-1.2% of the mass
  • the crosslinking agent is selected from the group consisting of ethylene glycol dimethacrylate, N, N'-methylene diacrylate amine, N, N'-1,4-phenylene diacrylamide, pentaerythritol triacrylate One or more of ester, trimethoxypropane trimethacrylate.
  • step 1) after adding a polymer monomer, a lithium salt, a conductive particle, an initiator and a crosslinking agent to the solvent, the mixture is uniformly stirred at a rotation speed of 800-2000 r/min, and heated to 50-100 ° C.
  • Crosslinking polymerization is preferably carried out at 60 to 85 ° C to form a polymer network structure encapsulating the lithium salt and the conductive particles.
  • step 3 the solvent is removed by vacuum drying at 50-70 ° C to form a solid electrolyte.
  • the solvent is at least one selected from the group consisting of propylene carbonate, dimethylpropionamide, acetonitrile, and ⁇ -butyrolactone.
  • the present invention also provides an all-solid battery comprising a positive electrode, a negative electrode and a solid electrolyte, characterized in that:
  • the solid electrolyte is the solid electrolyte of the present invention.
  • Conductive particles are included in the positive electrode and/or the negative electrode, the conductive particles matching the spatial configuration of the channels.
  • the present invention has the following advantages:
  • the solid electrolyte of the present invention is polymerized by molecular imprinting technology, has a porous channel for facilitating ion shuttle, and greatly improves the ionic conductivity of the all-solid electrolyte;
  • the surface of the solid electrolyte of the present invention has pores left after the conductive particles are eluted, provides selective embedding sites for the conductive particles on the surface of the positive and negative electrodes, increases the interface compatibility with the positive and negative pole pieces, and reduces the interface. impedance;
  • the pores left after the elution of the conductive particles on the solid electrolyte of the present invention facilitate ion shuttle, and do not cause micro short circuit of the battery formed by perforation of the electrolyte membrane.
  • the solid electrolyte of the invention can be applied to batteries such as lithium ion batteries, lithium sulfur batteries and lithium air batteries, and can solve the problem that the existing all solid state batteries have low conductivity due to solid electrolyte and poor compatibility between solid electrolyte and electrode interface, interface impedance. The problem caused by the large battery electrical performance degradation.
  • FIG. 1 is a schematic view of a solid electrolyte according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of an all solid state battery in accordance with an embodiment of the present invention.
  • the present invention provides a solid electrolyte having pores having a spatial configuration matching the conductive particles and having a specific recognition function for the conductive particles.
  • the channel facilitates the shuttle of ions, greatly improves the ionic conductivity of the solid electrolyte, and does not cause micro-short circuit of the battery formed by perforation of the electrolyte membrane, and can provide selective embedding sites for the conductive particles on the positive and negative electrodes of the battery.
  • the interface compatibility between the positive and negative pole pieces is increased, and the interface impedance is reduced, thereby solving the battery electrical performance of the existing all solid state battery due to low conductivity of the solid electrolyte and poor compatibility between the solid electrolyte and the electrode interface, and large interface impedance. The problem of falling.
  • the solid electrolyte of the present embodiment can be applied to a battery such as a lithium ion battery, a lithium sulfur battery, and a lithium air battery.
  • polymer monomer and lithium salt are used as functional monomers
  • conductive particles are used as template molecules
  • initiator and crosslinker are added and dissolved in solvent, stirred and mixed at 800-2000r/min, and the mixture is heated.
  • Cross-linking polymerization is carried out at 50-100 ° C (preferably 80 ° C) to form a polymer network structure encapsulating the lithium salt and the conductive particles, and then the conductive particles in the polymer network structure are washed away by using an eluent at 50-70.
  • the solvent is removed by vacuum drying at ° C to form a solid electrolyte having pores having a specific recognition function for the conductive particles.
  • the polymer monomer, the lithium salt, the conductive particles, the initiator and the crosslinking agent are dissolved in a solvent, and stirred and mixed uniformly at a rotation speed of 800-2000 r/min, they are poured into a mold to be heated and polymerized, and eluted by elution.
  • the agent can form a solid electrolyte membrane after washing the conductive particles.
  • molds of different thicknesses may be selected, generally preferably 80-100 ⁇ m, typically but not limited to 80um, 85um, 90um, 95um and 100um.
  • the above stirring speed is preferably 1000-1500 r/min, typically but not limited to 1000 r/min, 1100 r/min, 1150 r/min, 1200 r/min, 1250 r/min, 1300 r/min. 1,350 r/min, 1400 r/min, 1450 r/min, 1500 r/min, wherein the most preferred value is 1200 r/min.
  • the heating temperature is preferably 60-85 ° C, typically but not limited to 60 ° C, 63 ° C, 65 ° C, 68 ° C, 70 ° C, 73 ° C, 75 ° C, 78 ° C, 80 ° C, 82 ° C and 85 ° C, preferably A preferred value is 80 °C.
  • the temperature for vacuum drying is typically, but not limited to, 50 ° C, 52 ° C, 55 ° C, 58 ° C, 60 ° C, 62 ° C, 65 ° C, 68 ° C and 70 ° C, most preferably 60 ° C.
  • Molecular imprinting is a process of transferring various biomacromolecules from a gel to a fixed substrate.
  • the basic principle is that when the template molecule (imprinted molecule) contacts the polymer monomer, multiple action points are formed. This effect of the process is memorized.
  • the template molecule is removed, a hole with multiple points of action matching the spatial configuration of the template molecule is formed in the polymer. Such holes will be applied to the template molecule and the like.
  • the object has a selective recognition characteristic.
  • the molecular imprinting technique has the following characteristics: 1. Predetermination, that is, it can prepare different imprinted polymer MIPs according to different purposes to meet various needs. 2. Identification, that is, the imprinted polymer MIPs are customized according to the template molecule, and the imprinted molecules can be specifically identified. 3. Practicality, that is, it can be compared with natural biomolecular recognition systems such as enzymes and substrates, antigens and antibodies, receptors and hormones, but since it is prepared by chemical synthesis, it has natural molecular recognition. The system's ability to withstand harsh environments, resulting in high stability and long life.
  • the conductive particles in the present embodiment are in contact with the polymer monomer and the lithium salt, multiple action points are formed, and cross-linking polymerization occurs under the action of the crosslinking agent and the initiator, and these multiple action points are memorized during the polymerization process.
  • the conductive particles 2 are eluted by the eluent, holes having multiple action points matching the spatial configuration of the conductive particles are formed in the polymer, and such holes have selective recognition for the conductive particles and the like. .
  • the polymer monomer mainly plays a supporting role in the electrolyte membrane.
  • the polymer monomer is selected from one or more of ethylene oxide, acrylonitrile, vinylidene fluoride, methyl methacrylate, propylene oxide, and vinylidene chloride. These polymer monomers, after mixing with the initiator and crosslinker, are heated to initiate polymerization to form the corresponding polymer network structure.
  • the lithium salt mainly functions as a lithium ion to migrate and conduct electricity in the electrolytic reaction system.
  • the lithium salt is selected from lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, lithium bisfluorosulfonimide, lithium trifluoromethylsulfonimide, lithium oxalate difluoroborate, bis(pentafluorobenzene)
  • One or more of lithium ethyl sulfonyl imide and lithium dioxalate borate One or more of lithium ethyl sulfonyl imide and lithium dioxalate borate.
  • the conductive particles are one or more selected from the group consisting of carbon nanotubes (CNT), conductive graphite, conductive carbon black, and ketjen black.
  • CNT carbon nanotubes
  • conductive graphite SP-Li conductive graphite SP-Li
  • conductive carbon black KS6, Ketchen black ECP and the like.
  • the conductive particles can be selected according to actual needs, such as the specific conditions of the positive and negative pole pieces.
  • Carbon nanotubes generally have a diameter of about 5 nm and a length of 10-20 ⁇ m. They not only act as "wires" in the conductive network, but also have an electric double layer effect, which exhibits high rate characteristics of supercapacitors and good thermal conductivity. The performance is also beneficial for heat dissipation during battery charging and discharging, reducing the polarization of the battery, improving the high and low temperature performance of the battery, and prolonging the life of the battery.
  • the conductive graphite SP-Li has a small particle size and is similar to the conductive carbon black, but the specific surface area is moderate, especially in the form of a branch in the battery, which is very advantageous for forming a conductive network, and has the disadvantage that it is difficult to disperse.
  • Conductive carbon black KS6 is used as a conductive additive in lithium ion electrodes to make up for the deficiency of conductive graphite.
  • Conductive carbon black KS6 has small particle size, large specific surface area, and excellent electrical conductivity. It can act as liquid absorption and liquid retention in batteries. The shortcoming is that the price is high and it is difficult to disperse.
  • Ketchen Black ECP is a carbon black made from a very original and special production process. Compared with ordinary conductive carbon black, Ketchen Black ECP has a unique branch-like morphology. The advantage of this form is that the conductive contacts have many conductive contacts, and the branches form more conductive paths, so only a few additions are required. The amount of electricity can be extremely high (other carbon blacks are mostly spherical or flake-shaped, so a high amount of addition is required to achieve the desired electrical properties). Inco Black's ECP's ultra-high conductivity, its use is much less than other conductive carbon black, so it can fill more active substances, greatly improving the battery's current density and battery capacity, thus extending battery life It is especially suitable for high-end lithium batteries.
  • Ketchen Black ECP is that the resistance of the battery during charging and discharging does not increase due to volume changes. This is because the branched form of the Ketchen Black ECP is sufficient between the active substance and the active substance. Contact does not lose contact due to changes in the gap.
  • the finally formed solid electrolyte has a pore having a specific recognition function for the conductive particles, and the pore diameter is correspondingly 5 to 40 nm.
  • the prepared solid electrolyte forms a pore having a recognition function, and the pore diameter is controlled to be 10-30 nm.
  • the particle diameter of the conductive particles is typically, but not limited to, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm; the pore diameters are correspondingly, but not limited to, preferably 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, and 40 nm.
  • the mass of the initiator is from 0.6 to 1.2%, preferably from 0.8 to 1.1%, based on the total mass of the polymer monomers, typically but not limited to 0.6%, 0.7%, 0.8%, 0.9%, 1.0. %, 1.1% and 1.2%.
  • a compound which is easily decomposed into a radical (ie, a primary radical) when heated can be used as an initiator, can be used for initiating radical polymerization and copolymerization of an ethylenic or diene monomer, and can also be used for crosslinking of an unsaturated polyester. Curing and polymer crosslinking reaction.
  • a radical ie, a primary radical
  • the initiator may be selected from low activity azobisisobutyronitrile and/or azobisisoheptanenitrile.
  • azobisisobutyronitrile is used in a temperature range of 50-65 ° C, and is uniformly decomposed, forming only one kind of free radical, no other side reaction, relatively stable, and can be safely stored in a pure state, but also rapidly decomposed at 80-90 ° C.
  • the disadvantage is that the decomposition rate is low, and the formed isobutyronitrile radical lacks the dehydrogenation ability, so it cannot be used as an initiator for graft polymerization.
  • the azobisisoheptanenitrile has a large activity and high initiating efficiency, and can replace azobisisobutyronitrile, preferably azobisisoheptanenitrile. Since dimethyl azobisisobutyrate (AIBME) has moderate activity, easy polymerization, no residue in the polymerization process, high product conversion rate and harmless decomposition products, it is the best substitute for azobisisobutyronitrile. .
  • AIBME dimethyl azobisisobutyrate
  • Crosslinking agent is one of the important factors for the successful preparation of molecularly imprinted membranes. It can improve the cross-linking degree of molecularly imprinted polymers, and the host-guest complex formed by imprinted molecules and functional monomers can maintain a good shape in the polymer. To form a memory hole structure.
  • the degree of crosslinking of the imprinted polymer is too high, it will lead to difficulty in elution and recovery of the imprinted molecules, especially for some expensive imprinted molecules, and a large loss;
  • the degree of association makes the accessibility of the imprinting site worse, and the mass transfer rate is lowered, so that the practical application of the molecular imprinting technique is limited. Therefore, the type and amount of the cross-linking agent are the key to the molecular imprinting method.
  • the crosslinking agent may be selected from ethylene glycol dimethacrylate, N, N'-methylene diacrylamide, N, N'-1,4-phenylene diacrylamide, and pentaerythritol.
  • ethylene glycol dimethacrylate is inexpensive, easy to purify, and the molecularly imprinted polymer produced is stable in performance, it can be preferably used as the crosslinking agent of the present embodiment.
  • the molar ratio of functional monomer to EDMA is generally maintained at a level of 1:5.
  • N,N'-methylene diacrylate, N,N'-1,4-phenylene diacrylamide, trimethoxypropane trimethacrylate, 3,5 diacrylamide Benzoic acid, divinylbenzene, pentaerythritol triacrylate, and the like are also commonly used crosslinking agents.
  • the ratio of template molecules to functional monomers has a large effect on the generation of holes in the molecularly imprinted membrane.
  • the functional monomer and its ratio to the template molecule should be appropriately selected according to the type of functional group possessed by the template molecule and the nature of the solvent system in the molecularly imprinted membrane preparation process.
  • the ratio of functional monomer to crosslinker has a large effect on the performance of the blotting membrane.
  • the molar ratio of template molecule, functional monomer (mixture of polymer monomer to lithium salt) and crosslinker is 1-5:20-100:4-30, typically but not limited to 1: 20:4, 1:30:4, 1:40:4, 1:50:4, 1:60:4, 1:70:4, 1:80:4, 1:90:4, 1:100: 4, 1:50:5, 1:50:10, 1:50:20 and 1:50:30, wherein the molar ratio of the polymer monomer in the functional monomer to the lithium in the lithium salt is 6-8 :1, typically but not limited to 6:1, 7:1 and 8:1.
  • the molar ratio of the template molecule, the functional monomer and the crosslinking agent is preferably 2-4:30-76:10-25, and the polymer monomer in the functional monomer
  • the molar ratio of the body to lithium in the lithium salt is preferably from 6.8 to 7.8:1.
  • the solvent may be one selected from the group consisting of propylene carbonate, dimethyl acrylamide, acetonitrile, and ⁇ -butyrolactone. These solvents have high polarity and are capable of dissolving enough of the above lithium salt to obtain high electrical conductivity.
  • the amount of the solvent to be added may be sufficient to completely dissolve the lithium salt, and the specific amount may be appropriately added depending on the amount of the lithium salt to be added.
  • the eluent may be one or more selected from the group consisting of chloroform, 1,2-dichlorobenzene, methylnaphthalene, and 1-bromo-2-methylnaphthalene.
  • butanol may also be selected.
  • Other reagents such as ethylene glycol capable of dissolving the above-mentioned conductive particles, after washing off the conductive particles, form holes having multiple action points matching the spatial configuration of the conductive particles used to selectively recognize such conductive particles and the like Things.
  • the added eluent needs to be excessive so that the conductive particles can be sufficiently eluted to elute the conductive particles from the polymer network structure to form a pore structure.
  • a specific embodiment is provided, wherein a polymer monomer ethylene oxide (EO) and a lithium salt LiTFSI are used as functional monomers, and a CNT (particle size of about 8 nm) is used as a template molecule, and an initiator azobisisotin is added.
  • the nitrile and the cross-linking agent EDMA are dissolved in the solvent acetonitrile for cross-linking polymerization, and the CNTs are washed away by the eluent chloroform, (heating polymerization in a template having a thickness of 90 ⁇ m, elution, solvent removal) to form a polycyclic ring having a thickness of 90 ⁇ m.
  • Oxyethane (PEO)-based solid electrolyte A (1) which has a pore size 3 of about 8 nm pore size which has a specific recognition function for the conductive particles 2 of the CNT and is equivalent to the particle diameter of the CNT (see the figure). 1).
  • the present embodiment further provides an all-solid battery comprising the above-described PEO-based solid electrolyte A, positive electrode tab B, negative electrode tab C, and aluminum plastic film D.
  • the preparation method of the all-solid battery is as follows:
  • the positive electrode active material contained in the positive electrode piece is lithium cobaltate (LCO), lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminate (NCA), lithium iron phosphate (LFP), and manganese acid.
  • LCO lithium cobaltate
  • NCM lithium nickel cobalt manganese oxide
  • NCA lithium nickel cobalt aluminate
  • LFP lithium iron phosphate
  • MSO lithium cobaltate
  • LCM lithium nickel cobalt manganese oxide
  • NCA lithium nickel cobalt aluminate
  • LFP lithium iron phosphate
  • the positive electrode active material 4 has a mass ratio of 70-99.9%;
  • the conductive agent is one or more of CNT, graphene, conductive graphite, conductive carbon black, Ketjen black ECP, carbon fiber (VGCF), and the proportion of the conductive agent 0.1-15%;
  • the binder is one of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), fluorinated rubber, polyurethanekind or several, the binder ratio is 0.1-15%.
  • the negative electrode active material contained in the negative electrode piece 5 is artificial graphite, natural graphite, mesophase carbon microsphere, hard carbon, soft carbon, lithium titanate (LTO), silicon-based negative electrode, tin-based negative electrode, graphite One or more of aene, metallic lithium, and zinc alloy, preferably artificial graphite.
  • the negative electrode active material 5 has a mass ratio of 70-99.9%;
  • the conductive agent is one or more of CNT, graphene, conductive graphite, conductive carbon black, Ketjen black ECP, VGCF, and the conductive agent has a mass ratio of 0.1-15. %;
  • the binder is one or more of PVDF, PVA, CMC, SBR, fluorinated rubber, polyurethane, and the binder ratio is 0.1-15%.
  • Aluminum plastic film mainly comprises an outer nylon layer, an intermediate aluminum layer and an inner layer PP layer composite composition.
  • the above-mentioned components A-D are fabricated into finished batteries according to a conventional battery process, and after being statically divided and divided, a rechargeable battery (all-solid battery) is prepared.
  • the PEO-based solid electrolyte A has a channel 3 left after elution of the CNT, and the conductive particles, preferably CNT, are provided to the surface of the positive and negative electrodes.
  • Selective embedding sites increase the interfacial compatibility with the positive and negative pole pieces, thereby reducing the interface impedance and improving the electrical performance of the battery, especially the rate performance.
  • step 1) is first carried out: a functional monomer, a conductive particle, an initiator and a crosslinking agent are added to the solvent for cross-linking polymerization, and the functional monomer includes a polymer monomer and a lithium salt to form a encapsulated lithium salt. And a polymer network structure of the conductive particles; wherein the molar ratio of the conductive particles, the functional monomer and the crosslinking agent is 1:20:4, wherein between the polymer monomer in the functional monomer and the lithium in the lithium salt The molar ratio is 6:1.
  • the polymer monomer is ethylene oxide
  • the conductive particles are carbon nanotubes
  • the carbon nanotubes have a particle diameter of 20 nm.
  • the lithium salt is lithium bistrifluoromethylsulfonimide.
  • the initiator is azobisisobutyronitrile and the mass of the initiator is 1% by mass of the polymer monomer.
  • the crosslinking agent is ethylene glycol dimethacrylate and the solvent is acetonitrile.
  • step 2) is carried out: the carbon nanotubes in the polymer network structure are washed away by using an eluent to form pores in the polymer network structure; the eluent is chloroform.
  • step 3) is performed to remove acetonitrile to obtain a solid electrolyte.
  • the solid electrolyte has pores, and the pores have a spatial configuration matched with the carbon nanotubes, and can specifically identify conductive particles such as carbon nanotubes, wherein vacuum drying at 60 ° C removes acetonitrile. Solid electrolyte.
  • steps 1) to 3) were carried out in a mold having a thickness of 85 ⁇ m, and finally a solid electrolyte membrane having a thickness of 83 ⁇ m was formed.
  • This example was identical to Example 1 except that the molar ratio between the polymer monomer in the functional monomer and the lithium in the lithium salt was 7:1.
  • Example 2 The other conditions were the same for this example compared to Example 1, except that the molar ratio between the polymer monomer in the functional monomer and the lithium in the lithium salt was 8:1.
  • Example 2 This example is identical to Example 1 except that the polymer monomer is acrylonitrile.
  • This example is identical to Example 1 except that the polymer monomer is vinylidene fluoride.
  • This example is the same as in Example 1, except that the conductive particles are conductive graphite.
  • This example is the same as in Example 1, except that the conductive particles are conductive carbon black.
  • the comparative conditions were the same as in Example 1, except that no conductive particles were added in step 1) and step 2) was absent.
  • This comparative example was identical to Example 2 except that no conductive particles were added in step 1) and step 2) was absent.
  • Example 3 The comparative conditions were the same as in Example 3 except that no conductive particles were added in step 1) and step 2) was absent.
  • Example 4 The comparative conditions were the same as in Example 4 except that no conductive particles were added in step 1) and step 2) was absent.
  • Example 5 The comparative conditions were the same as in Example 5 except that no conductive particles were added in step 1) and step 2) was absent.
  • Example 6 The comparative conditions were the same as in Example 6, except that no conductive particles were added in step 1) and step 2) was absent.
  • Example 7 The comparative conditions were the same as in Example 7, except that no conductive particles were added in step 1) and step 2) was absent.
  • the comparative conditions were the same as in Example 8, except that no conductive particles were added in step 1) and step 2) was absent.
  • Example 9 The comparative conditions were the same as in Example 9, except that no conductive particles were added in step 1) and step 2) was absent.
  • Examples 10-18 provide an all solid state battery, respectively, using the solid electrolyte provided in Examples 1-9 as a solid electrolyte.
  • Conductive particles are included in the positive electrode and the negative electrode, and the conductive particles are matched to the spatial configuration of the cells, and are the conductive particles used in the production methods of Examples 1 to 9, respectively.
  • the all solid state batteries of Examples 10 to 18 include a solid electrolyte, a positive electrode tab, a negative electrode tab, and an aluminum plastic film.
  • the positive electrode active material contained in the positive electrode tab is nickel cobalt cobalt manganate (NCM), and the mass ratio of the positive electrode active material is 80%; the conductive agent is the conductive particles used in the preparation methods of Examples 1 to 9, respectively.
  • the conductive agent has a mass ratio of 10%; the binder is polyvinylidene fluoride (PVDF), which accounts for 10%.
  • the negative electrode active material contained in the negative electrode tab is artificial graphite, and the proportion is 80%; the conductive agent is the conductive particles used in the preparation methods of Examples 1 to 9, respectively, and the conductive agent has a mass ratio of 10%; the binder is PVDF. The binder ratio is 10%.
  • Aluminum plastic film mainly consists of outer layer nylon layer, intermediate aluminum layer and inner layer PP layer composite composition.
  • the above components are fabricated into finished batteries according to a conventional battery process, and after standing and dispersing, an all-solid battery is prepared.
  • Comparative Examples 10 to 18 were the same as those of Examples 10 to 18 except that the solid electrolytes provided in Comparative Examples 10 to 18, respectively, in Comparative Examples 1 to 9 were solid electrolytes.
  • the all-solid batteries in Examples 10-18 and 10-18 were subjected to rate discharge tests at 25 ° C, and the discharge currents were 0.1 C, 0.2 C, 0.5 C, and 1 C, respectively, and the charge and discharge voltage range was 4.2-3.0 V. .
  • the results of the measured rate retention ratio are shown in Table 1.
  • Examples 10 to 18 have the use of the solid electrolyte of the present invention, which has pores, which improves the ionic conductivity of the solid electrolyte and reduces the ionic conductivity of the solid electrolyte.
  • the interfacial resistance between the electrode and the solid electrolyte increases the rate performance of the all-solid-state battery using it.

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Abstract

一种固态电解质(1)，所述固态电解质(1)具有孔道(3)，孔道(3)具有与导电粒子(2)相匹配的空间构型以特定识别导电粒子(2)。所述固态电解质(1)的制备方法，包括步骤：1)在溶剂中加入功能单体、导电粒子(2)、引发剂和交联剂进行交联聚合，功能单体包括聚合单体和锂盐，形成包裹锂盐和导电粒子(2)的聚合物网络结构；2)利用洗脱剂将聚合物网络结构内的导电粒子(2)洗除；3)去除溶剂得到固态电解质(1)，固态电解质(1)具有孔道(3)，孔道(3)具有与导电粒子(2)相匹配的空间构型以特定识别导电粒子(2)。一种全固态电池，包括正极片、负极片和所述固态电解质(1)。所述固态电解质(1)离子电导率高，与正负极界面的相容性强，界面阻抗小，使用其的全固态电池电性能大大提高。

Description

固态电解质及其制备方法和全固态电池
本申请要求于2017年12月29日提交的题为“固态电解质及其制备方法和全固态电池”的中国专利申请号201711487472.4的优先权，其全部内容通过引用并入本文。
技术领域
本发明属于电池领域，具体涉及固态电解质及其制备方法，以及包括该固态电解质的全固态电池。
背景技术
近年来，随着电信、电动车等产业的快速发展，动力、储能等用途的可充电式蓄电池也呈现快速增长。全球环保要求的提高和电动车等新型交通工具的发展，将推动着诸如锂离子电池、锂硫电池以及锂空气电池等电池产业的迅速发展。然而可充电式蓄电池在实际应用过程中却存在着一定的安全问题，主要是因其中的有机电解液易发生挥发、泄露，容易诱发着火、爆炸等安全事故。
以固态电解质制成的全固态电池，采用固态电解质作为离子导体实现正负极活性物质之间锂离子的传递，同时可以作为隔膜分隔正负极防止内部短路，极大的提高了蓄电池的安全性能。
然而，固态电解质存在与电极界面之间的相容性差、界面阻抗大、离子电导率低等问题，限制了固态电池的研究进展。
因此，研究和开发与电极界面高相容性及高性能的固态电解质已成为可充电式蓄电池发展的关键所在。
发明内容
(一)要解决的技术问题
为了解决现有技术的上述问题，本发明的目的之一是提供一种具有 高离子电导率，与正负极界面高度相容性，减小界面阻抗以提高电池电性能的固态电解质。
本发明的目的之二是提供一种上述固态电解质的制备方法。
本发明的目的之三是提供一种包括上述固态电解质的全固态电池。
(二)技术方案
为了达到上述目的，本发明采用的主要技术方案包括：
根据本发明的目的之一，提供一种固态电解质，所述固态电解质具有孔道，所述孔道具有与导电粒子相匹配的空间构型以特定识别所述导电粒子。
优选地，所述孔道的孔径与所述导电粒子的粒径相匹配。
优选地，所述孔道的孔径为5-40nm，且所述导电粒子的粒径为5-40nm。
优选地，所述导电粒子选自碳纳米管、导电石墨、导电炭黑、科琴黑中的一种或几种。
优选地，所述固态电解质包括：锂盐、和包裹所述锂盐的聚合物网络结构；其中，所述孔道位于所述聚合物网络结构中。
优选地，形成所述聚合物网络结构的聚合物单体选自环氧乙烷、丙烯腈、偏氟乙烯、甲基丙烯酸甲酯、环氧丙烷和偏氯乙烯中的一种或几种。
优选地，形成所述聚合物网络结构的聚合物单体与所述锂盐中的锂之间的摩尔比为6-8:1。
根据本发明的目的之二，提供一种固态电解质的制备方法，所述固态电解质采用分子印迹技术以聚合物单体和锂盐为功能单体，导电粒子作为模板分子，加入引发剂和交联剂并溶于溶剂中进行交联聚合，包括以下步骤：
1)在溶剂中加入功能单体、导电粒子、引发剂和交联剂进行交联聚合，所述功能单体包括聚合物单体和锂盐，形成包裹所述锂盐和所述导 电粒子的聚合物网络结构；
2)利用洗脱剂将所述聚合物网络结构内的所述导电粒子洗除，在所述聚合物网络结构中形成孔道；和
3)去除溶剂得到固态电解质，所述固态电解质具有孔道，所述孔道具有与所述导电粒子相匹配的空间构型以特定识别所述导电粒子。
优选地，所述导电粒子、功能单体及交联剂的摩尔比为1-5:20-100:4-30，其中，功能单体中的聚合物单体与锂盐中的锂的摩尔比为6-8:1。
优选地，所述聚合物单体选自环氧乙烷、丙烯腈、偏氟乙烯、甲基丙烯酸甲酯、环氧丙烷和偏氯乙烯中的一种或几种。
优选地，所述导电粒子选自碳纳米管、导电石墨、导电炭黑、科琴黑中的一种或几种。
优选地，所述导电粒子的粒径为5-40nm，所述孔道的孔径为5-40nm。
优选地，所述锂盐选自六氟磷酸锂、六氟砷酸锂、四氟硼酸锂、高氯酸锂、双氟磺酰亚胺锂、三氟甲基磺酰亚胺锂、草酸二氟硼酸锂、双(五氟乙基磺酰)亚胺锂、二草酸硼酸锂中的一种或几种。
优选地，所述洗脱剂选自氯仿、1,2-二氯苯、甲基萘、1-溴-2-甲基萘、丁醇、乙二醇中的一种或几种。
优选地，所述引发剂选自偶氮二异丁腈、偶氮二异庚腈和偶氮二异丁酸二甲酯中的至少一种，所述引发剂质量占所述聚合物单体质量的0.6-1.2％
优选地，所述交联剂选自乙二醇二甲基丙烯酸酯、N，N’-亚甲基二丙烯酸胺、N，N’-1，4-亚苯基二丙烯酰胺、季戊四醇三丙烯酸酯、三甲氧基丙烷三甲基丙烯酸酯中的一种或几种。
优选地，在步骤1)中，在溶剂中加入聚合物单体、锂盐、导电粒子、引发剂和交联剂后，以800-2000r/min的转速搅拌混合均匀，加热到50-100℃，优选60-85℃进行交联聚合，形成包裹所述锂盐和所述导电粒 子的聚合物网络结构。
优选地，在步骤3)中，在50-70℃下真空干燥去除溶剂形成固态电解质。
优选地，所述溶剂选自碳酸丙烯酯、二甲基丙酰胺、乙腈、γ-丁内酯中的至少一种。
根据本发明的目的之三，本发明还提供了一种全固态电池，包括正极、负极、固态电解质，其特征在于：
所述固态电解质为本发明所述的固态电解质；且
在所述正极和/或所述负极中包括导电粒子，所述导电粒子与所述孔道的空间构型相匹配。
(三)有益效果
与现有技术相比，本发明具有以下优点：
1、本发明的固态电解质采用分子印迹技术聚合而成，具有利于离子穿梭的多孔通道，极大地提高了全固态电解质的离子电导率；
2、本发明的固态电解质表面具有导电粒子洗脱后留下的孔道，给正负极表面的导电粒子提供选择性嵌入位点，增加与正负极极片的界面相容性，减小界面阻抗；
3、本发明固态电解质上导电粒子洗脱后留下的孔道利于离子的穿梭，且不会造成因电解质膜穿孔而形成的电池微短路。
4、本发明的固态电解质可应用于锂离子电池、锂硫电池和锂空气电池等蓄电池中，可解决现有全固态电池因固态电解质电导率低以及固态电解质与电极界面相容性差、界面阻抗大造成的电池电性能下降的问题。
附图说明
图1为根据本发明一种实施方式的的固态电解质示意图；
图2为根据本发明一种实施方式的全固态电池的示意图。
图中：
1、固态电解质；2、导电粒子；3、孔道；4、正极活性物质；5、负 极活性物质。
具体实施方式
为了更好的解释本发明，以便于理解，下面结合附图，通过具体实施方式，对本发明作详细描述。
本发明提出一种固态电解质，该固态电解质具有孔道，孔道具有与导电粒子相匹配的空间构型，并对导电粒子有特定识别功能。
孔道有利于离子的穿梭，极大地提高固态电解质的离子电导率，且不会造成因电解质膜穿孔而形成的电池微短路，同时能够给电池正负极表面的导电粒子提供选择性嵌入位点，增加与正负极极片的界面相容性，减小界面阻抗，从而解决了现有全固态电池因固态电解质电导率低以及固态电解质与电极界面相容性差、界面阻抗大造成的电池电性能下降的问题。
本实施方式的固态电解质可应用于锂离子电池、锂硫电池和锂空气电池等蓄电池中。
采用分子印迹技术以聚合物单体及锂盐为功能单体，导电粒子作为模板分子，加入引发剂和交联剂并溶于溶剂中，以800-2000r/min的转速搅拌混合均匀，加热混合物到50-100℃(优选80℃)进行交联聚合，形成包裹锂盐和导电粒子的聚合物网络结构，然后再利用洗脱剂将聚合物网络结构内的导电粒子洗除，在50-70℃下真空干燥去除溶剂后形成具有对导电粒子有特定识别功能的孔道的固态电解质。
当将聚合物单体、锂盐、导电粒子、引发剂和交联剂溶于溶剂中，以800-2000r/min的转速搅拌混合均匀后，将其倒入模具中进行加热聚合，用洗脱剂将导电粒子洗除后可以形成固态电解质膜。
制备不同厚度的固态电解质膜，可以选择不同厚度的模具，一般优选80-100μm，典型但非限制性地优选80um、85um、90um、95um和100um。
为了提高制备效率，降低成本，上述的搅拌速度优选为1000-1500r/min，典型但非限制性地优选1000r/min、1100r/min、1150r/min、 1200r/min、1250r/min、1300r/min、1350r/min、1400r/min、1450r/min、1500r/min，其中，最佳优选值为1200r/min。
加热温度优选60-85℃，典型但非限制性地优选60℃、63℃、65℃、68℃、70℃、73℃、75℃、78℃、80℃、82℃和85℃，最佳优选值为80℃。
真空干燥的温度典型但非限制性地优选50℃、52℃、55℃、58℃、60℃、62℃、65℃、68℃和70℃，最佳优选值为60℃。
分子印迹技术是将各种生物大分子从凝胶转移到一种固定基质上的过程，其基本原理为：当模板分子(印迹分子)与聚合物单体接触时会形成多重作用点，通过聚合过程这种作用就会被记忆下来，当模板分子除去后，聚合物中就形成了与模板分子空间构型相匹配的具有多重作用点的空穴，这样的空穴将对模板分子及其类似物具有选择识别特性。
分子印迹技术具有以下几个特性：1.预定性，即它可以根据不同的目的制备不同的印迹聚合物MIPs，以满足各种不同的需要。2.识别性，即印迹聚合物MIPs是按照模板分子定制的，可专一地识别印迹分子。3.实用性，即它可以与天然的生物分子识别系统如酶与底物、抗原与抗体、受体与激素相比拟，但由于它是由化学合成的方法制备的，因此又有天然分子识别系统所不具备的抗恶劣环境的能力，从而表现出高度的稳定性和长的使用寿命。
本实施方式中的导电粒子与聚合物单体和锂盐相接触时会形成多重作用点，在交联剂和引发剂的作用下发生交联聚合反应，在聚合过程中这些多重作用点被记忆下来，当导电粒子2被洗脱剂洗脱后，聚合物中形成与导电粒子空间构型相匹配的具有多重作用点的空穴，这样的空穴对导电粒子及其类似物具有选择识别性。
在本实施方式中，聚合物单体在电解质膜中主要起到支撑作用。聚合物单体选自环氧乙烷、丙烯腈、偏氟乙烯、甲基丙烯酸甲酯、环氧丙烷和偏氯乙烯中的一种或几种。这些聚合物单体在与引发剂和交联剂混合后，加热引发聚合反应，形成对应的聚合物网络结构。
锂盐在电解反应体系中主要起锂离子迁移导电的作用。锂盐选自六氟磷酸锂、六氟砷酸锂、四氟硼酸锂、高氯酸锂、双氟磺酰亚胺锂、三氟甲基磺酰亚胺锂、草酸二氟硼酸锂、双(五氟乙基磺酰)亚胺锂、二草酸硼酸锂中的一种或几种。
导电粒子选自碳纳米管(CNT)、导电石墨、导电炭黑、科琴黑中的一种或几种。例如，导电石墨SP-Li、导电炭黑KS6、科琴黑ECP等。可根据实际需要，例如正负极极片的具体情况来选择导电粒子。
碳纳米管一般直径在5nm左右，长度达到10-20μm，它不仅能够在导电网络中充当“导线”的作用，同时它还具有双电层效应，发挥超级电容器的高倍率特性，其良好的导热性能还有利于电池充放电时的散热，减少电池的极化，提高电池的高低温性能，延长电池的寿命。
导电石墨SP-Li粒径小，和导电炭黑差不多，但是比表面积适中，特别是它在电池中以支链形式存在，对形成导电网络十分有利，缺点是难以分散。
导电炭黑KS6作为导电添加剂用在锂离子电极中，弥补了导电石墨的不足，导电炭黑KS6粒径小，比表面积特别大，导电性特别好，在电池中它可以起到吸液保液的作用，缺点是价格高，难以分散。
科琴黑ECP是一种由极具原创性的特殊生产工艺所制得的炭黑。与普通的导电炭黑相比，科琴黑ECP具有独特的支链状形态，这种形态的优点在于，导电体导电接触点多，支链形成较多导电通路，因而只需很少的添加量即可达到极高的导电率(其他炭黑多为圆球状或片状，故需要很高的添加量才能达到所需的电性)。因科琴黑ECP的超高的导电性，其使用量比其它导电碳黑少很多，因而可以填充更多的活性物质，大大提高了电池的电流密度和电池容量，因而可延长电池的使用时间，特别适用于高端的锂电池，也可用于镍氢电池、干电池等其他类型的电池中提高产品的品质和耐久性，在超级电容器和许多导电、屏蔽材料中也有良好的应用效果。此外，科琴黑ECP的另一个特有的优点是，电池在充放 电过程中电阻不会因为体积的变化而增加，这是因为科琴黑ECP的支链状形态，与活性物质之间有充分接触，不会因为间隙的变化而失去接触。
当选择粒径为5-40nm的导电粒子时，最终形成的固态电解质具有对导电粒子有特定识别功能的孔道，孔径相应地为5-40nm。
当导电粒子的粒径研磨至10-30nm时，制备出的固态电解质形成的对其有识别功能的孔道，孔径则相应控制在10-30nm。
其中，导电粒子的粒径典型但非限制性地优选5nm、10nm、15nm、20nm、25nm、30nm、35nm、40nm；孔径相应地典型但非限制性地优选5nm、10nm、15nm、20nm、25nm、30nm、35nm和40nm。
在本实施方式中，引发剂的质量占聚合物单体总质量的0.6-1.2％，优选为0.8-1.1％，典型但非限制性地优选0.6％、0.7％、0.8％、0.9％、1.0％、1.1％和1.2％。
当受热时容易分解成自由基(即初级自由基)的化合物可作为引发剂，可用于引发烯类、双烯类单体的自由基聚合和共聚反应，也可用于不饱和聚酯的交联固化和高分子交联反应。
在这里，引发剂可选用低活性的偶氮二异丁腈和/或偶氮二异庚腈。其中，偶氮二异丁腈的使用温度范围50～65℃，分解均匀，只形成一种自由基，无其他副反应，比较稳定，纯粹状态可安全储存，但在80～90℃也急剧分解，其缺点是分解速率较低，形成的异丁腈自由基缺乏脱氢能力，故不能用作接枝聚合的引发剂。而偶氮二异庚腈活性较大，引发效率高，可以取代偶氮二异丁腈，优选偶氮二异庚腈。由于偶氮二异丁酸二甲酯(AIBME)引发活性适中，聚合反应易控，聚合过程无残渣，产品转化率高，分解产物无害，因此是偶氮二异丁腈的最佳替代品。
交联剂是成功制备分子印迹膜的重要因素之一，它可提高分子印迹聚合物的交联度,使印迹分子与功能单体形成的主客体配合物能够在聚合物中保持较好的形状以形成记忆的空穴结构。但需要阐明的是，若印迹聚合物的交联度太高，将导致印迹分子的洗脱与回收变得困难，特别 对于某些昂贵的印迹分子，会造成很大的损失；同时高的交联度使印迹位点的可接近性变差，使传质速率降低，从而使分子印迹技术的实际应用受到限制，因此交联剂的种类和用量选择是分子印迹法制膜的技术关键。
在本实施方式中，交联剂可选择乙二醇二甲基丙烯酸酯，N，N’-亚甲基二丙烯酸胺、N，N’-1，4-亚苯基二丙烯酰胺、季戊四醇三丙烯酸酯、三甲氧基丙烷三甲基丙烯酸酯中的一种或几种。
由于乙二醇二甲基丙烯酸酯(EDMA)的价格便宜，容易纯化，而且制备的分子印迹聚合物性能稳定，因此，可优先选择其作为本实施方式的交联剂。为了制备高度交联的分子印迹聚合物以形成规整性好的记忆空穴，功能单体与EDMA的摩尔比一般保持在1:5的水平。除此之外，N，N’-亚甲基二丙烯酸胺、N，N’-1，4-亚苯基二丙烯酰胺、三甲氧基丙烷三甲基丙烯酸酯、3,5二丙烯酰胺基苯甲酸、二乙烯基苯、季戊四醇三丙烯酸酯等也是常用的交联剂。
模板分子与功能单体的比例对分子印迹膜中识别空穴的产生有很大影响。应根据模板分子所具有的功能基团的种类，以及分子印迹膜制备过程溶剂体系的性质，适当的选择功能单体及其与模板分子的比例。另外，功能单体和交联剂的比例对印迹膜性能的影响也很大。当交联剂的浓度偏低时，膜液就达不到足够的交联度，无法保持空穴的稳定的构型，也就不能表现出应有的识别能力，但过高又会使单位体积膜液含有功能单体的数目降低，影响膜识别效率。
经实验优化，模板分子、功能单体(聚合物单体与锂盐的混合物)及交联剂的摩尔比为1-5:20-100:4-30，典型但非限制性地优选1:20:4、1:30:4、1:40:4、1:50:4、1:60:4、1:70:4、1:80:4、1:90:4、1:100:4、1：50:5、1:50:10、1:50:20和1:50:30，其中，功能单体中的聚合物单体与锂盐中的锂的摩尔比为6-8:1，典型但非限制性地优选6:1、7:1和8:1。
为了降低成本，提高制备效率，获得电性能良好的电解质，模板分 子、功能单体及交联剂的摩尔比优选为2-4:30-76:10-25，功能单体中的聚合物单体与锂盐中锂的摩尔比优选为6.8-7.8:1。
溶剂可选择碳酸丙烯酯、二甲基丙烯酰胺、乙腈、γ-丁内酯中的一种，这些溶剂的极性高，能够溶解足够的上述锂盐，得到高的电导率。溶剂添加量以能够充分地将锂盐溶解完全即可，具体的量可根据选择的锂盐添加量来适当添加。
在本实施方式中，洗脱剂可选择氯仿、1,2-二氯苯、甲基萘、1-溴-2-甲基萘中的一种或几种，当然，还可以选择丁醇、乙二醇等能够溶解上述导电粒子的其他试剂，洗除导电粒子后，形成与使用的导电粒子空间构型相匹配的具有多重作用点的空穴，以选择性识别此类导电粒子及其类似物。添加的洗脱剂需要过量，以便能够充分地溶出导电粒子，将导电粒子从聚合物网络结构中洗脱出，从而形成孔道结构。
现提供一具体的实施方式，以聚合物单体环氧乙烷(EO)及锂盐LiTFSI为功能单体，以CNT(粒径约为8nm)作为模板分子，加入引发剂偶氮二异丁腈和交联剂EDMA并溶于溶剂乙腈进行交联聚合，利用洗脱剂氯仿将CNT洗除，(在厚度为90um的模板中加热聚合、洗脱，除溶剂)形成厚度为90μm的聚环氧乙烷(PEO)基固态电解质A(1)，该PEO基固态电解质A(1)具有对CNT的导电粒子2有特定识别功能且与CNT粒径相当的约8nm孔径的孔道3(参见图1)。
上述PEO基固态电解质A的具体制备过程如下：
将功能单体EO及双三氟甲基磺酰亚胺锂(LiTFSI)、模板分子CNT、交联剂乙二醇二甲基丙烯酸酯按照CNT:EO:LiTFSI:乙二醇二甲基丙烯酸酯3:35:5:20摩尔比加入至溶剂乙腈中混合，之后加入质量占EO质量1％的引发剂偶氮二异丁腈，以1200r/min的搅拌速度搅拌混合均匀后，将混合物加热到80℃进行交联聚合，形成包裹有锂盐及CNT且具有聚合物网络结构的PEO基固态电解质，然后再使用过量的洗脱剂氯仿将PEO基聚合物网络结构内部的CNT洗除，在60℃下真空干燥去除乙腈后，形 成具有对CNT有特定识别功能的孔道的PEO基固态电解质A。
此外，本实施方式还提供一种全固态电池，包括上述的PEO基固态电解质A、正极极片B、负极极片C和铝塑膜D。全固态电池的制备方法具体如下：
B、正极极片：正极极片包含的正极活性物质4为钴酸锂(LCO)、镍钴锰酸锂(NCM)、镍钴铝酸锂(NCA)、磷酸铁锂(LFP)、锰酸锂(LMO)、富锂锰基、氧气、硫元素中的一种或几种，优选NCM。正极活性物质4的质量占比为70-99.9％；导电剂为CNT、石墨烯、导电石墨、导电碳黑、科琴黑ECP、碳纤维(VGCF)中一种或几种，导电剂质量占比为0.1-15％；粘结剂为聚偏氟乙烯(PVDF)、聚乙烯醇(PVA)、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)、氟化橡胶、聚氨酯中的一种或几种，粘结剂占比为0.1-15％。
C、负极极片：负极极片包含的负极活性物质5为人造石墨、天然石墨、中间相炭微球、硬碳、软碳、钛酸锂(LTO)、硅基负极、锡基负极、石墨烯、金属锂、锌合金中一种或几种，优选人造石墨。负极活性物质5质量占比为70-99.9％；导电剂为CNT、石墨烯、导电石墨、导电碳黑、科琴黑ECP、VGCF中一种或几种，导电剂质量占比为0.1-15％；粘结剂为PVDF、PVA、CMC、SBR、氟化橡胶、聚氨酯中的一种或几种，粘结剂占比为0.1-15％。
D、铝塑膜：主要包括外层尼龙层，中间铝层以及内层PP层复合组成。
将上述组件A-D按照常规电池工艺制成成品电芯，经过静置分容后，制备可充电式蓄电池(全固态电池)。
如图2所示，当正极、负极与全固态电解质组装成全固态电池时，该PEO基固态电解质A具有CNT洗脱后留下的孔道3，给正负极表面的导电粒子，优选CNT，提供选择性嵌入位点，增加与正负极极片的界面相容性，从而减小界面阻抗，可提升该电池的电性能，尤其是倍率性能。
下面结合实施例对本发明的固态电解质的制备方法做进一步的描述，但本发明实施例仅用于对本发明进行说明，并不会对本发明的保护范围进行限制。
实施例1
在该实施例中，首先进行步骤1)：在溶剂中加入功能单体、导电粒子、引发剂和交联剂进行交联聚合，功能单体包括聚合物单体和锂盐，形成包裹锂盐和导电粒子的聚合物网络结构；其中，导电粒子、功能单体和交联剂的摩尔比为1:20:4，其中，功能单体中的聚合物单体与锂盐中的锂之间的摩尔比为6:1。聚合物单体为环氧乙烷，导电粒子为碳纳米管，碳纳米管的粒径为20nm。锂盐为双三氟甲基磺酰亚胺锂。引发剂为偶氮二异丁腈，引发剂的质量占聚合物单体质量的1％。交联剂为乙二醇二甲基丙烯酸酯，溶剂为乙腈。
在乙腈中加入环氧乙烷、双三氟甲基磺酰亚胺锂、碳纳米管、偶氮二异丁腈和乙二醇二甲基丙烯酸酯后，以1500r/min的转速搅拌混合均匀，加热到80℃进行交联聚合，形成包裹双三氟甲基磺酰亚胺锂和碳纳米的聚合物网络结构。
之后进行步骤2)：利用洗脱剂将聚合物网络结构内的碳纳米管洗除，在聚合物网络结构中形成孔道；洗脱剂为氯仿。
最后进行步骤3)，去除乙腈得到固态电解质，固态电解质具有孔道，孔道具有与碳纳米管相匹配的空间构型，能够特定识别导电粒子如碳纳米管，其中在60℃下真空干燥去除乙腈形成固态电解质。
其中，步骤1)～3)在厚度为85um的模具中进行，最后形成厚度为83um的固态电解质膜。
实施例2
该实施例与实施例1相比，其它条件均相同，除了导电粒子、功能单体及交联剂的摩尔比为1:50:20。
实施例3
该实施例与实施例1相比，其它条件均相同，除了导电粒子、功能单体及交联剂的摩尔比为3:60:25。
实施例4
该实施例与实施例1相比，其它条件均相同，除了功能单体中的聚合物单体与锂盐中的锂之间的摩尔比为7:1。
实施例5
该实施例与实施例1相比，其它条件均相同，除了功能单体中的聚合物单体与锂盐中的锂之间的摩尔比为8:1。
实施例6
该实施例与实施例1相比，其它条件均相同，除了聚合物单体为丙烯腈。
实施例7
该实施例与实施例1相比，其它条件均相同，除了聚合物单体为偏氟乙烯。
实施例8
该实施例与实施例1相比，其它条件均相同，除了导电粒子为导电石墨。
实施例9
该实施例与实施例1相比，其它条件均相同，除了导电粒子为导电炭黑。
对比例1
该对比例与实施例1相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例2
该对比例与实施例2相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例3
该对比例与实施例3相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例4
该对比例与实施例4相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例5
该对比例与实施例5相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例6
该对比例与实施例6相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例7
该对比例与实施例7相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例8
该对比例与实施例8相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
对比例9
该对比例与实施例9相比，其它条件均相同，除了在步骤1)中未加导电粒子，以及不存在步骤2)。
实施例10～18
实施例10-18分别提供一种全固态电池，分别以实施例1-9提供的固态电解质为固态电解质。在正极和负极中包括导电粒子，导电粒子与孔道的空间构型相匹配，且分别为实施例1～9的制备方法中采用的导电粒子。
实施例10～18中的全固态电池，包括固态电解质、正极极片、负极极片和铝塑膜。
正极极片：正极极片包含的正极活性物质为镍钴锰酸锂(NCM)，正极活性物质的质量占比为80％；导电剂分别为实施例1～9的制备方法中采用的导电粒子，导电剂质量占比为10％；粘结剂为聚偏氟乙烯(PVDF)，占比为10％。
负极极片包含的负极活性物质为人造石墨，占比为80％；导电剂分别为实施例1～9的制备方法中采用的导电粒子，导电剂质量占比为10％；粘结剂为PVDF，粘结剂占比为10％。
铝塑膜：主要包括外层尼龙层，中间铝层以及内层PP层复合组成。
将上述组件按照常规电池工艺制成成品电芯，经过静置分容后，制备全固态电池。
对比例10～18
对比例10～18的其它条件与实施例10～18均相同，不同之处在于对比例10-18分别以对比例1-9提供的固态电解质为固态电解质。
将实施例10-18与对比例10-18中的全固态电池均在25℃进行倍率放电测试，放电电流分别为0.1C、0.2C、0.5C及1C，充放电电压范围为4.2-3.0V。测得倍率保持率的结果如表1所示。
表1
Figure PCTCN2018119157-appb-000001
Figure PCTCN2018119157-appb-000002
根据表1中实施例10～18和对比例10～18的检测结果可以看出，实施例10～18由于采用了本发明的固态电解质，具有孔道，提高了固态电解质的离子电导率，降低了电极和固态电解质之间的界面电阻，从而提高了采用其的全固态电池的倍率性能。
将实施例10与对比例10的数据直接对比，可以更明显的看出上述效果。
将其它实施例与其相对应的对比例的数据进行直接对比，也可以更明显的看出上述效果。
需要理解的是，以上对本发明的具体实施例进行的描述只是为了说明本发明的技术路线和特点，其目的在于让本领域内的技术人员能够了解本发明的内容并据以实施，但本发明并不限于上述特定实施方式。凡是在本发明权利要求的范围内做出的各种变化或修饰，都应涵盖在本发明的保护范围内。

Claims (20)

  1. 一种固态电解质，其特征在于：
    所述固态电解质具有孔道，所述孔道具有与导电粒子相匹配的空间构型以特定识别所述导电粒子。
  2. 根据权利要求1所述的固态电解质，其特征在于：
    所述孔道的孔径与所述导电粒子的粒径相匹配。
  3. 根据权利要求2所述的固态电解质，其特征在于：所述孔道的孔径为5-40nm，且所述导电粒子的粒径为5-40nm。
  4. 根据权利要求2所述的固态电解质，其特征在于：
    所述导电粒子选自碳纳米管、导电石墨、导电炭黑、科琴黑中的一种或几种。
  5. 根据权利要求1所述的固态电解质，其特征在于，所述固态电解质包括：锂盐、和包裹所述锂盐的聚合物网络结构；其中
    所述孔道位于所述聚合物网络结构中。
  6. 根据权利要求5所述的固态电解质，其特征在于，形成所述聚合物网络结构的聚合物单体选自环氧乙烷、丙烯腈、偏氟乙烯、甲基丙烯酸甲酯、环氧丙烷和偏氯乙烯中的一种或几种。
  7. 根据权利要求5所述的固态电解质，其特征在于，形成所述聚合物网络结构的聚合物单体与所述锂盐中的锂之间的摩尔比为6-8:1。
  8. 一种固态电解质的制备方法，其特征在于：包括步骤：
    1)在溶剂中加入功能单体、导电粒子、引发剂和交联剂进行交联聚合，所述功能单体包括聚合物单体和锂盐，形成包裹所述锂盐和所述导电粒子的聚合物网络结构；
    2)利用洗脱剂将所述聚合物网络结构内的所述导电粒子洗除，在所述聚合物网络结构中形成孔道；
    3)去除溶剂得到固态电解质，所述固态电解质具有孔道，所述孔道具有与所述导电粒子相匹配的空间构型以特定识别所述导电粒子。
  9. 根据权利要求8所述的制备方法，其特征在于：
    所述导电粒子、所述功能单体及交联剂的摩尔比为1-5:20-100:4-30，其中，所述功能单体中的聚合物单体与锂盐中的锂之间的摩尔比为6-8:1。
  10. 根据权利要求8所述的制备方法，其特征在于：
    所述聚合物单体选自环氧乙烷、丙烯腈、偏氟乙烯、甲基丙烯酸甲酯、环氧丙烷和偏氯乙烯中的一种或几种。
  11. 根据权利要求8所述的制备方法，其特征在于：
    所述导电粒子选自碳纳米管、导电石墨、导电炭黑、科琴黑中的一种或几种。
  12. 根据权利要求8所述的制备方法，其特征在于：
    所述导电粒子的粒径为5-40nm，所述孔道的孔径为5-40nm。
  13. 根据权利要求8所述的制备方法，其特征在于：
    所述锂盐选自六氟磷酸锂、六氟砷酸锂、四氟硼酸锂、高氯酸锂、双氟磺酰亚胺锂、三氟甲基磺酰亚胺锂、草酸二氟硼酸锂、双(五氟乙基磺酰)亚胺锂、二草酸硼酸锂中的一种或几种。
  14. 根据权利要求8所述的制备方法，其特征在于：
    所述洗脱剂选自氯仿、1,2-二氯苯、甲基萘、1-溴-2-甲基萘、丁醇、乙二醇中的一种或几种。
  15. 根据权利要求8所述的制备方法，其特征在于：
    所述引发剂选自偶氮二异丁腈、偶氮二异庚腈和偶氮二异丁酸二甲酯中的至少一种；
    所述引发剂的质量占所述聚合物单体质量的0.6-1.2％。
  16. 根据权利要求8所述的制备方法，其特征在于：所述交联剂选自乙二醇二甲基丙烯酸酯、N，N’-亚甲基二丙烯酸胺、N，N’-1，4-亚苯基二丙烯酰胺、季戊四醇三丙烯酸酯、三甲氧基丙烷三甲基丙烯酸酯中的至少一种。
  17. 根据权利要求8所述的制备方法，其特征在于：
    在步骤1)中，在溶剂中加入所述聚合物单体、锂盐、导电粒子、引发剂和交联剂后，以800-2000r/min的转速搅拌混合均匀，加热到50-100℃进行交联聚合，形成包裹所述锂盐和所述导电粒子的聚合物网络结构。
  18. 根据权利要求8所述的制备方法，其特征在于：
    在步骤3)中，在50-70℃下真空干燥去除溶剂形成固态电解质。
  19. 根据权利要求8所述的制备方法，其特征在于：
    所述溶剂选自碳酸丙烯酯、二甲基丙酰胺、乙腈、γ-丁内酯中的至少一种。
  20. 一种全固态电池，包括正极、负极、固态电解质，其特征在于：
    所述固态电解质为权利要求1-7中任一项所述的固态电解质；且
    在所述正极和/或所述负极中包括导电粒子，所述导电粒子与所述孔道的空间构型相匹配。
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