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CN106784547B - The preparation method of gel polymer lithium ion battery - Google Patents

The preparation method of gel polymer lithium ion battery Download PDF

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Publication number
CN106784547B
CN106784547B CN201611133513.5A CN201611133513A CN106784547B CN 106784547 B CN106784547 B CN 106784547B CN 201611133513 A CN201611133513 A CN 201611133513A CN 106784547 B CN106784547 B CN 106784547B
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graphene
lithium ion
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ion battery
nafion
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CN106784547A (en
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李睿
刘宾虹
李洲鹏
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
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    • Y02E60/10—Energy storage using batteries
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Abstract

本发明涉及凝胶锂离子电池的制备技术，旨在提供一种凝胶态聚合物锂离子电池的制备方法。包括：将单水葡萄糖、三聚氰胺、偏硼酸和NaCl‑KCl共晶盐球磨混合后，在氮气氛下经三次升温加热后冷至室温；用去离子水清洗掉盐分，真空干燥；将得到的石墨烯担载纳米硼与乙炔黑、Nafion‑PEO共混树脂溶液混合研磨，调制成膏状后涂敷到泡沫镍中；阴干后压制成型，得到负极；按正极、隔膜、负极的顺序排列、压制成型后，在氮气氛下热处理得到膜电极，在电解液中浸渍2小时得到电芯；以该电芯组装扣式凝胶态聚合物锂离子电池。本发明不存在游离态电解液，能显著提高锂离子电池的安全性，有利于电极结构的稳定，有利于大电流放电，为电动汽车提供安全可靠的高能动力电池。

The invention relates to a preparation technology of a gel lithium ion battery, and aims to provide a preparation method of a gel state polymer lithium ion battery. Including: after ball milling of glucose monohydrate, melamine, metaboric acid and NaCl-KCl eutectic salt, heating under nitrogen atmosphere for three times, and then cooling to room temperature; washing away the salt with deionized water, and vacuum drying; The alkene-supported nanoboron is mixed and ground with acetylene black and Nafion-PEO blended resin solution, prepared into a paste and then applied to nickel foam; after drying in the shade, it is pressed and formed to obtain a negative electrode; the order of positive electrode, separator and negative electrode is arranged and pressed. After forming, heat treatment in nitrogen atmosphere to obtain membrane electrodes, and immersion in electrolyte for 2 hours to obtain a battery cell; a button-type gel polymer lithium ion battery is assembled with the battery core. The invention has no free electrolyte, can significantly improve the safety of the lithium ion battery, is conducive to the stability of the electrode structure, is conducive to large current discharge, and provides a safe and reliable high-energy power battery for electric vehicles.

Description

The preparation method of gel polymer lithium ion battery
Technical field
The present invention relates to a kind of preparation methods of gel lithium ion battery, it is more particularly related to which gel state is poly- Close the preparation method of object lithium ion battery.
Background technique
Lithium ion battery has many advantages, such as that light-weight, capacity is big, memory-less effect, thus has obtained commonly used.Now Many digital equipments all use lithium ion battery and make power supply.The energy density of lithium ion battery is very high, its capacity is same 1.5~2 times of the nickel-metal hydride battery of weight, and have many advantages, such as very low self-discharge rate, be that it is answered extensively without noxious material Major reason.
So far, most of commercialized lithium ion batteries all use organic electrolyte solution as ion conducting layer. Using organic electrolyte solution, higher ionic conductivity can achieve, so that device is with good performance.But it is organic Electrolyte solution uses the product of excellent electrolytic solution, it is necessary to use firm gold there are solvent easy to leak, difficult the shortcomings that encapsulating Belong to shell, therefore the fixed shortage flexibility of gauge size.Electrolyte leakage not only results in component failure, organic solvent itself Inflammability will also result in the safety accidents such as burning, explosion.And safety is undoubtedly the primary index of product, arranges to the safety of battery Applying must be very perfect.In addition, current mobile electronic device to the miniaturization of energy storage device, lightening also proposed increasingly High requirement.Safety, No leakage, low pollution film-type energy storage device, especially film lithium ion battery causes widely Pay attention to.Gel electrolyte has good elasticity and good machining property, can be made into very thin film, is energy storage device Filming development provides advantage.
1973, Wright etc. had found that polyethylene glycol oxide (PEO) and alkali metal salt complexing have ionic conduction for the first time The phenomenon that, so that solid electrolytic Quality Research is entered a new stage, but the room-temperature conductivity and practical application of solid electrolyte It is required that apart from each other.In order to overcome the problems, such as this, Feuillade etc. first proposed gel electrolyte in 1975, later by Abraham etc. has made to further investigate the polymer network system that polymer gel is generally defined as one by solvent swell, Unique network structure makes gel while having the cohesiveness of solid and the dispersion conductibility of liquid.Nineteen ninety-five U.S. Bellcore Company discloses the technology that a kind of new type gel polymer dielectric is used to develop polymer Li-ion battery.Since then, to polymerization The object lithium ion battery base that gel electrolyte Quality Research polymer Li-ion battery in the ascendant is in liquid lithium ionic cell The latest generation lithium ion battery developed on plinth, constituting is the polymerization for using with ionic conductivity and having both diaphragm effect Object electrolyte replaces the electrolyte in liquid lithium ionic cell, and gel electrolyte is by polymer, plasticizer and lithium salts by one The gel polymeric network with appropriate microporous structure that fixed method is formed, utilizes the liquid electrolyte being fixed in micro-structure Molecule realizes ionic conduction.From 1975 gel polymer electrolyte (GPE) report for the first time since, there are many gel of system is poly- Polymer electrolyte has obtained exploitation to be studied with research more, better performances has following several types polymer: polyethylene glycol oxide (PEO) system, polyacrylonitrile (PAN) system, polymethyl methacrylate (PMMA) system and Kynoar (PVDF) system etc..There are also poly- Vinylpyrrolidone (PVP), polyethylene glycol (PFG) isogel electrolyte system.
Negative electrode material as gel polymer lithium ion battery must be have it is claimed below: (1) lithium storage capacity is high； (2) insertion, deintercalation reaction of the lithium in negative electrode material are fast, i.e. diffusion coefficient of the lithium ion in solid phase is big, in electrode-electric solution The mobile impedance at liquid interface is small；(3) existence of the lithium ion in electrode material is stablized；(4) in the charge and discharge cycles of battery In, negative electrode material volume change is small；(5) electron conduction is high；(6) negative electrode material and gel polymer electrolyte compatibility It is good.
Boron can reversible embedding lithium, the embedding lithium capacity of theory of boron is up to 3100mAh/g, is 8.34 times of graphite, is a kind of high Capacity lithium ion battery negative electrode material.Lithium titanate Li4Ti5O12It is a kind of composite oxygen by lithium metal and low potential transition metals Ti Compound belongs to AB2X4Series is described as spinel solid solution.
The spinel structure space group of lithium titanate is Fd3m space group, and it is non-conductive that cell parameter a, which is 0.836nm, White crystal, can be stabilized in air.Structure is similar to inverse spinel: in a structure cell, 32 negative oxygen ions O2-It is arranged by cubic closest packing, accounts for the lithium ion Li of sum 3/4+It is empty close to the insertion of positive tetrahedron ligand is made by four oxonium ions Gap, remaining lithium ion and all titanium ion Ti4+(atom number 1:5) is embedded in by six oxonium ions close to regular octahedron ligand is made Gap, Li4Ti5O12The channel of disengaging can be provided for limited lithium ion by stablizing fine and close structure.
Li4Ti5O12Maximum feature is exactly its " zero strain ".So-called " zero strain " refers to that its crystal is being embedded in or is taking off Lattice constant and volume change all very littles when lithium ion out, less than 1%.In charge and discharge cycles, this " zero strain " can It avoids leading to structural damage due to stretching back and forth for electrode material, so that the cycle performance and service life of electrode are improved, Circulation bring special capacity fade is reduced, there is extraordinary overcharging resisting, over-discharge feature.Lithium titanate material theoretical specific capacity is 175mAh/g has and has extended cycle life, high stability energy；Discharge platform is up to 1.55V, and platform is very flat.The disadvantage is that leading Electrically poor, heavy-current discharge polarization ratio is more serious, thus performance is bad under high magnification.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of gel polymer lithium The preparation method of ion battery.
In order to solve the technical problem, of the invention the specific scheme is that
A kind of preparation method of positive electrode for gel polymer lithium ion battery is provided, which is stone Black alkene supports a nanometer Li4Ti5O12, preparation the following steps are included:
(1) 30 grams of citric acids and 34 grams of butyl titanate are sequentially added in 300 milliliters of ethyl alcohol, ultrasonic disperse 40 divides Clock forms solution A；
(2) 50 grams of citric acids are added in 60 milliliters of ethyl alcohol, then 30 ml deionized waters and 5.28 grams is added thereto Lithium acetate forms B solution；
(3) solution A after temperature constant magnetic stirring 30 minutes, B solution is added dropwise in solution A, is obtained molten at 30 DEG C Glue；
(4) 10 grams of citric acids are added into colloidal sol obtained by step (3) makes the pH value 1.2 of colloidal sol, persistently stirs 1 hour, Obtain precursor sol；
(5) the mono- water glucose of 40g, 20g melamine and 300g NaCl-KCl eutectic salts are added into precursor sol, Paste is stirred into, obtained graphene supports a nanometer Li4Ti5O12Presoma；
(6) after obtained presoma being warming up to 110 DEG C of heating 2 hours under nitrogen atmosphere, 440 DEG C are warming up to after vacuumizing Heat preservation 8 hours is warming up to 800 DEG C and heats 2 hours, and heating rate is 10 DEG C/min three times；It then cools to room temperature, is contained Salt graphene supports a nanometer Li4Ti5O12；
(7) saliferous graphene is supported into a nanometer Li4Ti5O12Salinity is washed with deionized water, after vacuum drying, obtains stone Black alkene supports a nanometer Li4Ti5O12。
Invention further provides support a nanometer Li using graphene4Ti5O12Prepare gel polymer lithium ion electricity The method of the anode in pond, comprising steps of
(1) in mass ratio 80: 10: 100 graphene is taken to support a nanometer Li4Ti5O12, acetylene black, Nafion-PEO be blended tree Lipoprotein solution (Nafion is perfluorinated sulfonic resin, and the PEO is peo resin)；
(2) graphene is supported into a nanometer Li4Ti5O12, acetylene black, Nafion-PEO blending resin solution mixing, grinding, adjust It is coated in nickel foam after paste is made；In 100Kg/cm after drying in the shade2Pressure under compression moulding, obtain anode.
The present invention also provides the methods for preparing gel polymer lithium ion battery using the anode, including following steps It is rapid:
(1) the single water glucose of in mass ratio 4: 2: 1: 300 additions, melamine, metaboric acid and NaCl- in ball grinder KCl eutectic salts, with revolving speed 700rpm ball milling mixing 2 hours, obtained graphene supported the presoma of nanometer boron；
(2) after obtained presoma being warming up to 110 DEG C of heating 2 hours under nitrogen atmosphere, 440 DEG C are warming up to after vacuumizing After heat preservation 8 hours, it is warming up to 900 DEG C and heats 2 hours, heating rate is 10 DEG C/min three times；It then cools to room temperature, is contained Salt graphene supports a nanometer boron；
(3) saliferous graphene is supported into nanometer boron and washes salinity with deionized water, after vacuum drying, obtain graphene load Carry nanometer boron；
(4) in mass ratio 80: 10: 100 graphene is taken to support a nanometer boron, acetylene black, Nafion-PEO blending resin solution, Mixed grinding is coated in the nickel foam of city dealer after being modulated into paste；In 100Kg/cm after drying in the shade2Pressure under compression moulding, Obtain cathode；
(5) by the sequence arrangement of anode, diaphragm, cathode, in 100Kg/cm2Under pressure after compression moulding, in nitrogen atmosphere and 140 DEG C of heat treatments obtain membrane electrode for 2 hours, impregnate 2 hours in the electrolytic solution after cooling and obtain battery core；
(6) anode of battery core is placed in button cell shell and is contacted with battery case；In the negative side pad of battery core After the foam nickel sheet that upper diameter is 18mm, thickness 1mm, voidage are 98%, 0.5mL electrolyte is added, encrypts seal and battery cover After seal, obtain button gel polymer lithium ion battery；
The electrolyte is with LiPF6For solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is molten Agent；Wherein, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, contains 151.9 grams in one liter of electrolyte LiPF6。
In the present invention, the Nafion-PEO blending resin solution is prepared by following methods: in mass ratio Polyethylene glycol oxide (PEO, 5g) is added in the proton type perfluor sulfoacid resin solution (95g) of mass concentration 5wt% for 5: 95, is stirred Nafion-PEO blending resin solution is obtained after mixing dissolution.
In the present invention, the diaphragm is prepared by following methods: Nafion-PEO blending resin solution is fallen In horizontal glass plate, after solvent evaporation, the diaphragm of the 0.05mm thickness of formation.
In the present invention, the NaCl-KCl eutectic salts are prepared by following methods: 45:55 in mass ratio will Ball grinder was added in NaCl and KCl, with revolving speed 700rpm ball milling 1 hour；Then it is heated 2 hours at 700 DEG C, is cooled to 25 DEG C, obtains To NaCl-KCl eutectic salts.
Inventive principle description:
Present invention lithium titanate precursor gel as made from butyl titanate and lithium acetate and glucose, melamine, NaCl-KCl eutectic salts are uniformly mixed, and after calcining, are washed salinity with deionized water, are obtained graphene and support nanometer Li4Ti5O12As the positive electrode of gel polymer lithium ion battery, by glucose, melamine, metaboric acid and NaCl- KCl eutectic salts ball milling mixing washes with water salinity after calcining, obtains graphene and supports nanometer boron as the negative of battery Pole material is that base absorbs lithium-ion battery electrolytes using the blend of type lithium ion perfluorinated sulfonic resin and polyethylene glycol oxide Gel is the gel polymer lithium ion battery of electrolyte.Boron has high storage lithium specific capacity, and theoretical capacity is reachable 3100mAh/g.Volume change is quite big before and after the embedding lithium of boron when charge and discharge, and graphene has very high intensity and flexibility, can buffer The volume change of the embedding lithium of boron, to reduce the influence to electrode structure.
Cathode of the invention supports a nanometer boron using graphene, in the nafion-PEO blending resin and positive and negative anodes of diaphragm Blending resin combines together, forms 3 dimension contiguous networks.In subsequent electrolyte dipping process, electrolyte is distributed along three-dimensional network To between the graphene layer of electrode, liquid film is formed；Lithium ion exchanged occurs simultaneously, so that proton type perfluorosulfonic acid resin (nafion) turns It is melted into type lithium ion perfluorinated sulfonic resin.Li occurs for anode when charging4Ti5O12De- lithium process, lithium ion along three-dimensional network pass It is defeated to arrive cathode, the process of intercalation of boron occurs, forms boron lithium alloy.The mobile reverse of lithium ion when electric discharge, the lithium deintercalation in boron lithium, Lithium ion is transferred to anode along three-dimensional network, forms Li4Ti5O12。
Nanometer Li4Ti5O12In-situ preparation on nitrogenous graphene with boron, have very high activity, nitrogenous graphene with There are B-N keys between boron, so that boron particle is securely seated between on graphene.Graphene has very high electric conductivity, can be effective Improve Li4Ti5O12Electric conductivity.Graphene also has very high intensity and flexibility, therefore can effectively absorb when charge and discharge Volume change brought by the embedding lithium of boron.Nitrogen in nitrogenous graphene contains lone pair electrons as nucleophilic center, and whens charge and discharge is conducive to Electrolyte liquid film of the Li ion between graphene layer is uniformly distributed, to greatly reduce the ohmage of positive and negative anodes, to mention The performance of high-lithium ion battery.
In the present invention, when 110 DEG C of heating prepare positive electrode, glucose and melamine occur polymerization and generate glucose- Melamine resin and water, Li4Ti5O12Colloidal sol is dehydrated to form unformed Li4Ti5O12；When being warming up to 440 DEG C and preparing positive electrode In the process, carbonization takes place in glucose-urea resin；Li4Ti5O12Structure be changed into spinel structure by unformed； Glucose-the melamine resin being tentatively carbonized in 440 DEG C of insulating processes is coated on eutectic salts and spinel structure Li4Ti5O12On the particle of composition.800 DEG C are warming up to, carbonization after heating 2 hours is cooled to room temperature to obtain saliferous graphene Support a nanometer Li4Ti5O12；When glucose-melamine resin is carbonized, due to eutectic salts and nanometer Li4Ti5O12Space Blocking effect, glucose-melamine resin are carbonized to form graphene-structured；
In the present invention, in negative electrode material preparation process, it is warming up to 440 DEG C of glucose-trimerizations being tentatively carbonized in the process Melamine resin is coated on the particle of eutectic salts and metaboric acid composition.900 DEG C are warming up to, metaboric acid is reduced after heating 2 hours Boron is formed, is cooled to room temperature to obtain saliferous graphene and supports a nanometer boron；
In the present invention, membrane electrode is in 140 DEG C of heat treatment, the nafion-PEO blending resin of diaphragm and being total in positive and negative anodes Mixed resin combines together, forms 3 dimension contiguous networks.In subsequent electrolyte dipping process, electrolyte is distributed to along three-dimensional network It between the graphene layer of electrode, and is adsorbed by graphene, forms liquid film；Lithium ion exchanged occurs simultaneously, so that proton type fluosulfonic acid Resin (nafion) is converted to type lithium ion perfluorinated sulfonic resin.
Compared with prior art, the invention has the benefit that
Graphene of the invention supports nanometer boron lithium with good chemical stability, and boron has high storage lithium specific capacity Characteristic, diaphragm of the invention are Nafion-PEO blending resin, and the ability with very high Electolyte-absorptive has very high lithium Ionic conductivity；Nanometer Li4Ti5O12It is in-situ preparation on nitrogenous graphene with boron, there is very high activity, form one kind Gel polymer lithium ion battery.Since there is no free state electrolyte, the safety of lithium ion battery is significantly improved, is being contained The nanometer boron and Li formed between nitrogen graphene layer4Ti5O12, be conducive to the stabilization of electrode structure, the good electric conductivity of graphene has Conducive to heavy-current discharge, safe and reliable high-energy power battery is provided for electric car.
Detailed description of the invention
Fig. 1 is that graphene supports a nanometer Li4Ti5O12Transmission electron microscope photo.
Fig. 2 be in embodiment seven gel polymer lithium ion battery for preparing in 25 DEG C, the cyclic voltammetric of 0.2C rate Curve sets specific capacity as the embedding lithium capacity of theory of boron: C=3100mAh/g.
Appended drawing reference in Fig. 2 are as follows:
1 discharge curve, 2 charging curves.
Specific embodiment
It present invention will be described in detail below.
The preparation of one: NaCl-KCl eutectic salts of embodiment
NaCl (45g) and KCl (55g) are added ball grinder, ball milling 1 hour under revolving speed 700rpm, taking-up is put into crucible, empty It is heated 2 hours for 700 DEG C in gas, is cooled to 25 DEG C, obtains NaCl-KCl eutectic salts.
Embodiment two: graphene supports the preparation of nanometer boron
NaCl-KCl eutectic salts (30g) obtained in Example one, 4:2:1:300 in mass ratio is added in ball grinder Graphene is made in single water glucose, melamine, metaboric acid and NaCl-KCl eutectic salts, revolving speed 700rpm ball milling mixing 2 hours Support a nanometer presoma for boron lithium；
After being warming up to 110 DEG C of heating under nitrogen atmosphere 2 hours, after 440 DEG C of heat preservations being warming up to after vacuumizing 8 hours, heating It is heated 2 hours to 900 DEG C, heating rate is 10 DEG C/min three times, then cools to room temperature, obtains saliferous graphene and support nanometer Boron.It is dried in vacuo after washing salinity with deionized water, obtains graphene and support a nanometer boron.
The modulation of three: Nafion-PEO blending resin solution of embodiment
5g is added in the proton type perfluor sulfoacid resin solution of the mass content 5wt% of 95g DuPont Corporation production PEO (polyethylene glycol oxide) obtains Nafion-PEO blending resin solution after stirring and dissolving.
Example IV: diaphragm preparation
Nafion-PEO blending resin solution obtained in embodiment three is poured in horizontal glass plate, after solvent evaporation The Nafion-PEO blending resin film of the 0.05mm thickness of formation.
Embodiment five: the preparation of cathode
Graphene obtained supports in Example two modulates in a nanometer boron (0.8g), acetylene black (0.1g) and embodiment three Nafion-PEO blending resin solution (1g), graphene is supported into nanometer boron lithium alloy, acetylene black, a Nafion solution, by matter 80: 10: 100 mixed grindings of ratio are measured, are coated in city's dealer's nickel foam after being modulated into paste；In 100Kg/cm after drying in the shade2Pressure Lower compression moulding, obtains cathode.
Embodiment six: Li4Ti5O12The preparation of colloidal sol
Sequentially add 30 grams of citric acids and 34 grams of butyl titanate in 300 milliliters of ethyl alcohol, ultrasonic disperse 40 minutes, Form solution A；50 grams of citric acids are added in 60 milliliters of ethyl alcohol, then the second of 30 ml deionized waters and 5.28 grams is added thereto Sour lithium forms B solution.Solution A after temperature constant magnetic stirring 30 minutes, B solution is added dropwise in solution A, is obtained at 30 DEG C Colloidal sol；10 grams of citric acids are added in colloidal sol makes the pH value 1.2 of colloidal sol, persistently stirs 1 hour, obtains precursor sol.
Embodiment seven: graphene supports a nanometer Li4Ti5O12Preparation
The mono- water glucose of 40g, 20g melamine and 300g NaCl- is added in the precursor sol obtained in embodiment six KCl eutectic salts, stir into paste, and obtained graphene supports a nanometer Li4Ti5O12Presoma；It is warming up to 110 DEG C under nitrogen atmosphere After heating 2 hours, after 440 DEG C of heat preservations being warming up to after vacuumizing 8 hours, 800 DEG C of heating 2 hours are warming up to, three times heating rate For 10 DEG C/min, then cools to room temperature to obtain saliferous graphene and support a nanometer Li4Ti5O12.Salinity is washed with deionized water After be dried in vacuo, obtain graphene and support a nanometer Li4Ti5O12。
Embodiment eight: positive preparation
Graphene prepared by Example seven supports a nanometer Li4Ti5O12(0.8g), acetylene black (0.1g), embodiment three are made Standby Nafion-PEO blending resin solution (1g), supports a nanometer Li for graphene4Ti5O12, acetylene black, Nafion-PEO be blended Resin solution, in mass ratio 80: 10: 100 mixed grindings are coated in the nickel foam of city dealer after being modulated into paste；After drying in the shade 100Kg/cm2Pressure under compression moulding, obtain anode.
Embodiment nine: the assembling of button gel polymer lithium ion battery
By anode obtained in embodiment eight (taking diameter is the disk of 18mm), the diaphragm (diameter prepared in example IV It is placed on anode for 19mm)；Cathode obtained in embodiment three (taking diameter is the disk of 18mm) is placed on diaphragm； 100Kg/cm2Under pressure after compression moulding, in nitrogen atmosphere, 140 DEG C of heat treatments obtain membrane electrode for 2 hours, in electrolyte after cooling Middle dipping obtains battery core in 2 hours.The anode of battery core is placed in city dealer button cell shell (CR2025), is connect with battery case Touching；After the foam nickel sheet that diameter is 18mm on the negative side pad of battery core, thickness 1mm, voidage are 98%, 0.5mL electrolysis is added Liquid seals after encrypting seal and battery cover, obtains button gel polymer lithium ion battery.Electrolyte is with LiPF6For solute, The mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is solvent, ethylene carbonate: methyl carbonate: dimethyl carbonate Mass ratio be 4: 2: 4,151.9 grams of lithium hexafluoro phosphates are contained in one liter of electrolyte.
Embodiment ten: the charge and discharge of gel polymer lithium ion battery
When gel polymer lithium ion battery obtained in embodiment nine charges, Li occurs for anode4Ti5O12De- lithium mistake Process of intercalation occurs for the boron of journey, cathode, when the embedding full lithium of boron, charge cutoff.
When electric discharge, process of intercalation occurs in anode, and the deintercalation of lithium occurs for the boron lithium of cathode, when the lithium in boron lithium is all de- It is embedding, electric discharge cut-off.Fig. 2 is gel polymer lithium ion battery at 25 DEG C, and the cyclic voltammetry curve of 0.2C rate sets specific volume Amount is the embedding lithium capacity of theory of boron: C=3100mAh/g
The above enumerated are only specific embodiments of the present invention for finally, it should also be noted that.Obviously, the present invention is unlimited In above embodiments, acceptable there are many deformations.Those skilled in the art can directly lead from present disclosure Out or all deformations for associating, it is considered as protection scope of the present invention.

Claims (6)

1.用于凝胶态聚合物锂离子电池的正极材料的制备方法，其特征在于，该正极材料是石墨烯担载纳米Li4Ti5O12，其制备包括以下步骤：1. the preparation method of the positive electrode material for gel state polymer lithium ion battery, it is characterized in that, this positive electrode material is graphene-supported nanometer Li 4 Ti 5 O 12 , and its preparation comprises the following steps: (1)在300毫升乙醇中依次加入30克柠檬酸以及34克的钛酸四丁酯，超声分散40分钟，形成A溶液；(1) successively add 30 grams of citric acid and 34 grams of tetrabutyl titanate in 300 milliliters of ethanol, and ultrasonically disperse for 40 minutes to form A solution; (2)将50克柠檬酸加至60毫升乙醇中，再向其中加入30毫升去离子水和5.28克的乙酸锂形成B溶液；(2) 50 grams of citric acid was added to 60 milliliters of ethanol, and then 30 milliliters of deionized water and 5.28 grams of lithium acetate were added to form B solution; (3)将A溶液在30℃恒温磁力搅拌30分钟后，将B溶液逐滴加入到A溶液中，得到溶胶；(3) After the A solution was stirred at a constant temperature of 30°C for 30 minutes, the B solution was added dropwise to the A solution to obtain a sol; (4)向步骤(3)所得溶胶中添加10克柠檬酸使溶胶的pH值为1.2，持续搅拌1小时，得到前驱体溶胶；(4) adding 10 grams of citric acid to the sol obtained in step (3) to make the pH of the sol 1.2, and stirring continuously for 1 hour to obtain a precursor sol; (5)向前驱体溶胶中加入40g单水葡萄糖、20g三聚氰胺和300g NaCl-KCl共晶盐，搅拌成糊状，制得石墨烯担载纳米Li4Ti5O12的前驱体；(5) adding 40g of glucose monohydrate, 20g of melamine and 300g of NaCl-KCl eutectic salt to the precursor sol, stirring into a paste, to obtain a graphene-supported nano-Li 4 Ti 5 O 12 precursor; (6)将得到的前驱体在氮气氛下升温至110℃加热2小时后，抽真空后升温至440℃保温8小时，升温至800℃加热2小时，三次升温速度均为10℃/min；然后冷却至室温，得到含盐石墨烯担载纳米Li4Ti5O12；(6) after heating the obtained precursor to 110 ℃ for 2 hours under nitrogen atmosphere, after vacuuming, it is warmed to 440 ℃ and kept for 8 hours, then heated to 800 ℃ and heated for 2 hours, and the three heating rates are all 10 ℃/min; and then cooled to room temperature to obtain salt-containing graphene-supported nano-Li 4 Ti 5 O 12 ; (7)将含盐石墨烯担载纳米Li4Ti5O12用去离子水清洗掉盐分，真空干燥后，得到石墨烯担载纳米Li4Ti5O12。(7) The salt-containing graphene-supported nanometer Li 4 Ti 5 O 12 is washed with deionized water to remove the salt, and after vacuum drying, the graphene-supported nanometer Li 4 Ti 5 O 12 is obtained. 2.利用权利要求1所述方法得到的石墨烯担载纳米Li4Ti5O12制备凝胶态聚合物锂离子电池的正极的方法，其特征在于，包括步骤：2. the graphene-supported nano Li 4 Ti 5 O 12 obtained by the method of claim 1 prepares the method for the positive electrode of the gel state polymer lithium ion battery, it is characterized in that, comprises the steps: (1)按质量比80∶10∶100取石墨烯担载纳米Li4Ti5O12、乙炔黑、Nafion-PEO共混树脂溶液；(1) get graphene-supported nano-Li 4 Ti 5 O 12 , acetylene black, and Nafion-PEO blended resin solution at a mass ratio of 80:10:100; (2)将石墨烯担载纳米Li4Ti5O12、乙炔黑、Nafion-PEO共混树脂溶液混合、研磨，调制成膏状后涂敷到泡沫镍中；阴干后在100Kg/cm2的压力下压制成型，得到正极。(2) Mix and grind the graphene-supported nanometer Li 4 Ti 5 O 12 , acetylene black, and Nafion - PEO blended resin solution, prepare a paste, and apply it to the nickel foam; Press molding under pressure to obtain a positive electrode. 3.利用权利要求2所述方法得到的正极制备凝胶态聚合物锂离子电池的方法，其特征在于，包括下述步骤：3. the method that utilizes the positive electrode that the described method of claim 2 obtains to prepare gel state polymer lithium ion battery, is characterized in that, comprises the following steps: (1)在球磨罐中按质量比4∶2∶1∶300加入单水葡萄糖、三聚氰胺、偏硼酸和NaCl-KCl共晶盐，以转速700rpm球磨混合2小时，制得石墨烯担载纳米硼的前驱体；(1) add glucose monohydrate, melamine, metaboric acid and NaCl-KCl eutectic salt by mass ratio 4: 2: 1: 300 in the ball mill jar, and mix by ball milling at a rotating speed of 700rpm for 2 hours to obtain graphene-supported nano-boron precursor; (2)将得到的前驱体在氮气氛下升温至110℃加热2小时后，抽真空后升温至440℃保温8小时后，升温至900℃加热2小时，三次升温速度为10℃/min；然后冷却至室温，得到含盐石墨烯担载纳米硼；(2) after heating the obtained precursor to 110°C for 2 hours under nitrogen atmosphere, after vacuuming, it is heated to 440°C for 8 hours, then heated to 900°C for 2 hours, and the three heating rates are 10°C/min; Then cooled to room temperature to obtain salt-containing graphene-supported nanoboron; (3)将含盐石墨烯担载纳米硼用去离子水清洗掉盐分，真空干燥后，得到石墨烯担载纳米硼；(3) deionized water is used to clean the salt-containing graphene-loaded nano-boron, and after vacuum drying, graphene-loaded nano-boron is obtained; (4)按质量比80∶10∶100取石墨烯担载纳米硼、乙炔黑、Nafion-PEO共混树脂溶液，混合研磨，调制成膏状后涂敷到泡沫镍中；阴干后在100Kg/cm2的压力下压制成型，得到负极；(4) get graphene-supported nano-boron, acetylene black, Nafion-PEO blended resin solution by mass ratio of 80: 10: 100, mix and grind, modulate into paste and then apply to foam nickel; Compression molding under the pressure of cm 2 to obtain a negative electrode; (5)按正极、隔膜、负极的顺序排列，在100Kg/cm2压力下压制成型后，在氮气氛和140℃热处理2小时得到膜电极，冷却后在电解液中浸渍2小时得到电芯；(5) arranging in the order of positive electrode, diaphragm and negative electrode, press molding under 100Kg/cm 2 pressure, heat treatment in nitrogen atmosphere and 140 DEG C for 2 hours to obtain membrane electrode, and immerse in electrolyte for 2 hours after cooling to obtain cell; (6)将电芯的正极侧置于扣式电池外壳中且与电池外壳接触；在电芯的负极侧垫上直径为18mm、厚1mm、空隙率为98％的泡沫镍片后，加入0.5mL电解液，加密封圈和电池盖后密封，得到扣式凝胶态聚合物锂离子电池；(6) Place the positive side of the cell in the button battery case and contact the battery case; after padding the negative side of the cell with a nickel foam sheet with a diameter of 18mm, a thickness of 1mm and a porosity of 98%, add 0.5mL The electrolyte is sealed after adding a sealing ring and a battery cover to obtain a button-type gel polymer lithium ion battery; 所述电解液是以LiPF6为溶质，碳酸乙烯酯、碳酸甲酯与碳酸二甲酯的混和物为溶剂；其中，碳酸乙烯酯∶碳酸甲酯∶碳酸二甲酯的质量比为4∶2∶4，一升电解液中含151.9克LiPF6。Described electrolyte is to take LiPF 6 as a solute, and the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is a solvent; wherein, the mass ratio of ethylene carbonate: methyl carbonate: dimethyl carbonate is 4:2 : 4, one liter of electrolyte contains 151.9 grams of LiPF 6 . 4.根据权利要求2或3所述的方法，其特征在于，所述Nafion-PEO共混树脂溶液是通过下述方法制备获得的：按质量比为5∶95将聚氧化乙烯树脂加入质量浓度5wt％的质子型全氟磺酸树脂溶液中，搅拌溶解后得到Nafion-PEO共混树脂溶液。4. The method according to claim 2 or 3, wherein the Nafion-PEO blended resin solution is prepared by the following method: be 5: 95 by mass ratio by adding polyethylene oxide resin to mass concentration In the 5wt% proton type perfluorosulfonic acid resin solution, the Nafion-PEO blended resin solution is obtained after stirring and dissolving. 5.根据权利要求3所述的方法，其特征在于，所述隔膜是通过下述方法制备获得的：将Nafion-PEO共混树脂溶液倒在水平玻璃板上，待溶剂蒸发后，形成的0.05mm厚的隔膜。5. The method according to claim 3, wherein the diaphragm is prepared by the following method: pouring the Nafion-PEO blended resin solution on a horizontal glass plate, and after the solvent is evaporated, the formed 0.05 mm thick diaphragm. 6.根据权利要求1至3任意一项中所述的方法，其特征在于，所述NaCl-KCl共晶盐是通过下述方法制备获得的：按质量比45:55将NaCl和KCl加入球磨罐，以转速700rpm球磨1小时；然后在700℃加热2小时，冷却至25℃，得到NaCl-KCl共晶盐。6. according to the method described in any one of claim 1 to 3, it is characterised in that the NaCl-KCl eutectic salt is prepared by the following method: NaCl and KCl are added to ball milling by mass ratio 45:55 jar, ball milled at 700 rpm for 1 hour; then heated at 700° C. for 2 hours, cooled to 25° C. to obtain NaCl-KCl eutectic salt.
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