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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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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lithium ion
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李睿
刘宾虹
李洲鹏
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Zhejiang University ZJU
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Abstract

The present invention relates to the technologies of preparing of gel lithium ion battery, it is desirable to provide a kind of preparation method of gel polymer lithium ion battery.It include: to be cooled to room temperature after heating after single water glucose, melamine, metaboric acid and NaCl-KCl eutectic salts ball milling mixing, will be heated up three times under nitrogen atmosphere；Salinity is washed with deionized water, is dried in vacuo；Obtained graphene is supported into nanometer boron and acetylene black, Nafion-PEO blending resin solution mixed grinding, is coated in nickel foam after being modulated into paste；Compression moulding after drying in the shade, obtains cathode；After the sequence arrangement of anode, diaphragm, cathode, compression moulding, heat treatment obtains membrane electrode under nitrogen atmosphere, impregnates 2 hours obtain battery core in the electrolytic solution；Button gel polymer lithium ion battery is assembled with the battery core.Free state electrolyte is not present in the present invention, can significantly improve the safety of lithium ion battery, be conducive to the stabilization of electrode structure, be conducive to be large current discharge, safe and reliable high-energy power battery is provided for electric car.

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. the preparation method of the positive electrode for gel polymer lithium ion battery, which is characterized in that the positive electrode is Graphene 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 minutes, Form solution A；
(2) 50 grams of citric acids are added in 60 milliliters of ethyl alcohol, then the acetic acid of 30 ml deionized waters and 5.28 grams is added thereto Lithium forms B solution；
(3) solution A after temperature constant magnetic stirring 30 minutes, B solution is added dropwise in solution A, colloidal sol is obtained at 30 DEG C；
(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, obtains Precursor sol；
(5) the mono- water glucose of 40g, 20g melamine and 300g NaCl-KCl eutectic salts, stirring are added into precursor sol At paste, 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 of heat preservations are warming up to after vacuumizing It 8 hours, is warming up to 800 DEG C and heats 2 hours, heating rate is 10 DEG C/min three times；It then cools to room temperature, obtains saliferous stone Black alkene supports a nanometer Li4Ti5O12；
(7) saliferous graphene is supported into a nanometer Li4Ti5O12Salinity is washed with deionized water, after vacuum drying, obtains graphene Support a nanometer Li4Ti5O12。
2. supporting a nanometer Li using the graphene that claim 1 the method obtains4Ti5O12Prepare gel polymer lithium ion The method of the anode of battery, which is characterized in that comprising steps of
(1) in mass ratio 80: 10: 100 graphene is taken to support a nanometer Li4Ti5O12, acetylene black, Nafion-PEO blending resin it is molten Liquid；
(2) graphene is supported into a nanometer Li4Ti5O12, acetylene black, Nafion-PEO blending resin solution mixing, grinding, be modulated into It is coated in nickel foam after paste；In 100Kg/cm after drying in the shade2Pressure under compression moulding, obtain anode.
3. the method for preparing gel polymer lithium ion battery using the anode that claim 2 the method obtains, feature It is, includes the following steps:
(1) the single water glucose of in mass ratio 4: 2: 1: 300 additions, melamine, metaboric acid and NaCl-KCl are total in ball grinder Brilliant salt, 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 of heat preservations are warming up to after vacuumizing After 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, obtains saliferous stone Black alkene supports a nanometer boron；
(3) saliferous graphene is supported into nanometer boron and washes salinity with deionized water, after vacuum drying, obtain graphene and support to receive Rice 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 nickel foam 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 Heat treatment obtains membrane electrode for 2 hours, impregnates 2 hours in the electrolytic solution after cooling and obtains battery core；
(6) anode of battery core is placed in button cell shell and is contacted with battery case；It is straight on the negative side pad of battery core After the foam nickel sheet that diameter is 18mm, thickness 1mm, voidage are 98%, 0.5mL electrolyte is added, it is close after encryption seal and battery cover Envelope, obtains button gel polymer lithium ion battery；
The electrolyte is with LiPF6For solute, the mixture of ethylene carbonate, methyl carbonate and dimethyl carbonate is solvent；Its In, ethylene carbonate: methyl carbonate: the mass ratio of dimethyl carbonate is 4: 2: 4, contains 151.9 grams of LiPF in one liter of electrolyte6。
4. according to the method in claim 2 or 3, which is characterized in that the Nafion-PEO blending resin solution is to pass through What following methods prepared: the proton type that mass concentration 5wt% is added in peo resin for 5: 95 in mass ratio is complete Nafion-PEO blending resin solution is obtained in perfluorosulfonic acid resin solution, after stirring and dissolving.
5. according to the method described in claim 3, it is characterized in that, the diaphragm is prepared by following methods: will Nafion-PEO blending resin solution is poured in horizontal glass plate, after solvent evaporation, the diaphragm of the 0.05mm thickness of formation.
6. according to claim 1 to method described in 3 any one, which is characterized in that the NaCl-KCl eutectic salts are logical Cross what following methods prepared: ball grinder is added in NaCl and KCl by 45:55 in mass ratio, small with revolving speed 700rpm ball milling 1 When；Then it is heated 2 hours at 700 DEG C, is cooled to 25 DEG C, obtains NaCl-KCl eutectic salts.
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CN103588195A (en) * 2013-11-01 2014-02-19 天津大学 Preparation method of graphene
WO2016070396A1 (en) * 2014-11-07 2016-05-12 孙旭阳 Method for preparing graphene by molten state inorganic salt reaction bed

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CN102881882A (en) * 2012-10-15 2013-01-16 浙江大学 Preparation method and application of thin-wall capsule-shaped lithium titanate electrode material
CN103588195A (en) * 2013-11-01 2014-02-19 天津大学 Preparation method of graphene
WO2016070396A1 (en) * 2014-11-07 2016-05-12 孙旭阳 Method for preparing graphene by molten state inorganic salt reaction bed

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