CN106784547A - 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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CN106784547A
CN106784547A CN201611133513.5A CN201611133513A CN106784547A CN 106784547 A CN106784547 A CN 106784547A CN 201611133513 A CN201611133513 A CN 201611133513A CN 106784547 A CN106784547 A CN 106784547A
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graphene
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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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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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Abstract

The present invention relates to the technology of preparing of gel lithium ion battery, it is desirable to provide a kind of preparation method of gel polymer lithium ion battery.Including：After by single water glucose, melamine, metaboric acid and NaCl KCl eutectic salts ball milling mixings, it is cooled to room temperature after three heating that heat up under nitrogen atmosphere；Salinity is washed with deionized water, is vacuum dried；The Graphene that will be obtained supports nanometer boron and acetylene black, Nafion PEO blending resin solution mixed grindings, is coated in nickel foam after being modulated into paste；It is compressing after drying in the shade, obtain negative pole；By positive pole, barrier film, negative pole order arrangement, it is compressing after, membrane electrode is thermally treated resulting under nitrogen atmosphere, in the electrolytic solution dipping obtain battery core within 2 hours；Button gel polymer lithium ion battery is assembled with the battery core.The present invention does not exist free state electrolyte, can significantly improve the security of lithium ion battery, is conducive to the stabilization of electrode structure, is conducive to heavy-current discharge, for electric automobile provides safe and reliable high-energy power battery.

Description

The preparation method of gel polymer lithium ion battery
Technical field
The present invention relates to a kind of preparation method of gel lithium ion battery, it is more particularly related to gel state is poly- The preparation method of compound lithium ion battery.
Background technology
Lithium ion battery has the advantages that lightweight, capacity is big, memory-less effect, thus has obtained commonly used.Now Many digital equipments all employ lithium ion battery and make power supply.The energy density of lithium ion battery is very high, and its capacity is same 1.5~2 times of the Ni-MH battery of weight, and there is very low self-discharge rate, be that it extensively should 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, ionic conductivity higher can be reached so that device has good performance.But, it is organic Electrolyte solution haves the shortcomings that solvent easy to leak, difficult encapsulation, uses the product of excellent electrolytic solution, it is necessary to use firm gold Category shell, therefore gauge size fixes shortage flexibility.Electrolyte leakage not only results in component failure, and organic solvent is in itself Inflammability will also result in the security incidents such as burning, blast.And security is undoubtedly the primary index of product, the safety to battery is arranged Applying must be very perfect.Additionally, current mobile electronic device to the miniaturization of energy storage device, lightening it is also proposed increasingly Requirement high.Safety, No leakage, the film-type energy storage device of low stain, particularly film lithium ion battery are caused widely Pay attention to.Gel electrolyte has good elastic and good machining property, can be made into very thin film, is energy storage device Filming development provides advantage.
1973, Wright etc. was found that polyethylene glycol oxide (PEO) has ionic conduction with alkali metal salt complexing first Phenomenon, make solid electrolytic Quality Research enter a new stage, but solid electrolyte room-temperature conductivity and practical application It is required that apart from each other.In order to overcome this problem, Feuillade etc. to first proposed gel electrolyte in 1975, later by Abraham etc. has made further investigation polymer gels and has been generally defined as a polymer network system by solvent swell, its 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 a kind of new type gel polymer dielectric for developing the technology of polymer Li-ion battery.Since then, to polymerization Thing lithium ion battery gel electrolyte Quality Research polymer Li-ion batteries in the ascendant are the bases in liquid lithium ionic cell The latest generation lithium ion battery developed on plinth, its composition is to use with ionic conductivity and have concurrently the polymerization of barrier film effect Thing electrolyte replaces the electrolyte in liquid lithium ionic cell, and gel electrolyte is to pass through one by polymer, plasticizer and lithium salts The gel polymeric network with appropriate microporous structure that fixed method is formed, using the liquid electrolyte being fixed in micro-structural Molecule realizes ionic conduction.From 1975 gel polymer electrolyte (GPE) first report since, have various systems gel gather Polymer electrolyte has obtained exploitation more, better performances has following several types polymer with research researchs：Polyethylene glycol oxide (PEO) system, polyacrylonitrile (PAN) system, polymethyl methacrylate (PMMA) system and Kynoar (PVDF) system etc..Also gather Vinylpyrrolidone (PVP), polyethylene glycol (PFG) isogel electrolyte system.
Must possess claimed below as the negative material of gel polymer lithium ion battery：(1) lithium storage capacity is high； (2) soon, i.e., diffusion coefficient of the lithium ion in solid phase is big, in electrode-electric solution for insertion, deintercalation reaction of the lithium in negative material The mobile impedance at liquid interface is small；(3) existence stabilization of the lithium ion in electrode material；(4) in the charge and discharge cycles of battery In, negative material Volume Changes are small；(5) electron conduction is high；(6) negative material and gel polymer electrolyte compatibility It is good.
Boron can reversible embedding lithium, the theoretical embedding lithium capacity of boron is up to 3100mAh/g, is 8.34 times of graphite, is a kind of high Capacity lithium ion battery negative material.Lithium titanate Li4Ti5O12It is a kind of by lithium metal and the composite oxygen of 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 groups, and cell parameter a is 0.836nm, is non-conductive White crystal, in atmosphere can be with stable existence.Structure is similar to inverse spinel：In a structure cell, 32 negative oxygen ions O2-Arranged by cubic closest packing, account for the lithium ion Li of sum 3/4+It is empty close to the insertion of positive tetrahedron part is made by four oxonium ions Gap, remaining lithium ion and all titanium ion Ti4+(atom number 1:5) it is embedded in close to regular octahedron part is made by six oxonium ions Space, Li4Ti5O12The fine and close structure of stabilization can provide the passage of turnover for limited lithium ion.
Li4Ti5O12Maximum the characteristics of is exactly its " zero strain ".So-called " zero strain " refers to its crystal embedded or de- Lattice parameter and Volume Changes all very littles when going out lithium ion, less than 1%.In charge and discharge cycles, this " zero strain " can Avoid causing structural damage due to stretching back and forth for electrode material, so that the cycle performance and service life of electrode are improved, The special capacity fade of tape loop is reduced, with extraordinary overcharging resisting, is crossed and is put feature.Lithium titanate material theoretical specific capacity is 175mAh/g, with having extended cycle life, high stability energy；Discharge platform is up to 1.55V, and platform is very flat.Have the disadvantage to lead Electrically poor, heavy-current discharge polarization ratio is more serious, thus performance is not good under high magnification.
Invention Inner holds
The technical problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided a kind of gel polymer lithium The preparation method of ion battery.
To solve technical problem, concrete scheme of the invention is：
A kind of preparation method of positive electrode for gel polymer lithium ion battery is provided, the positive electrode is stone Black alkene supports a nanometer Li4Ti5O12, its preparation comprises the following steps：
(1) 30 grams of citric acids and 34 grams of butyl titanate, 40 points of ultrasonic disperse are sequentially added in 300 milliliters of ethanol Clock, forms solution A；
(2) in 50 grams of citric acids being added into 60 milliliters of ethanol, then 30 ml deionized waters and 5.28 grams are added thereto to Lithium acetate forms B solution；
(3) is added dropwise to B solution in solution A after 30 DEG C of temperature constant magnetic stirrings 30 minutes by solution A, obtains molten Glue；
(4) make the pH value of colloidal sol be 1.2 to 10 grams of citric acids of addition in step (3) gained colloidal sol, persistently stir 1 hour, Obtain precursor sol；
(5) to the mono- water glucose of addition 40g, 20g melamines and 300g NaCl-KCl eutectic salts in precursor sol, Pasty state is stirred into, prepared Graphene supports a nanometer Li4Ti5O12Presoma；
(6) presoma that will be obtained be warming up under nitrogen atmosphere 110 DEG C heating 2 hours after, 440 DEG C are warming up to after vacuumizing Insulation 8 hours, is warming up to 800 DEG C and heats 2 hours, and three times programming rate is 10 DEG C/min；Room temperature is subsequently cooled to, 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, stone is obtained Black alkene supports a nanometer Li4Ti5O12。
A nanometer Li is supported invention further provides using Graphene4Ti5O12Prepare gel polymer lithium ion electricity The method of the positive pole in pond, including step：
(1) in mass ratio 80: 10: 100 take Graphene and support a nanometer Li4Ti5O12, acetylene black, Nafion-PEO blending 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 resins solution mixing, grinding, adjust It is coated in nickel foam after being made paste；In 100Kg/cm after drying in the shade2Pressure under it is compressing, obtain positive pole.
Method present invention also offers gel polymer lithium ion battery is prepared using the positive pole, including following steps Suddenly：
(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 rotating speed 700rpm ball milling mixings 2 hours, prepared Graphene supported the presoma of nanometer boron；
(2) presoma that will be obtained be warming up under nitrogen atmosphere 110 DEG C heating 2 hours after, 440 DEG C are warming up to after vacuumizing After insulation 8 hours, it is warming up to 900 DEG C and heats 2 hours, three programming rates is 10 DEG C/min；Room temperature is subsequently cooled to, is contained Salt Graphene supports a nanometer boron；
(3) saliferous Graphene is supported into a nanometer boron deionized water and washes salinity, after vacuum drying, obtain Graphene load Carry nanometer boron；
(4) in mass ratio 80: 10: 100 take Graphene and 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 it is compressing, Obtain negative pole；
(5) arranged by the order of positive pole, barrier film, negative pole, in 100Kg/cm2Under pressure it is compressing after, in blanket of nitrogen and 140 DEG C of heat treatments obtain membrane electrode in 2 hours, are impregnated in the electrolytic solution after cooling 2 hours and obtain battery core；
(6) positive pole of battery core is placed in button cell shell and is contacted with battery case；In the negative side pad of battery core After upper a diameter of 18mm, thickness 1mm, the foam nickel sheet that voidage is 98%, 0.5mL electrolyte is added, encrypt seal and battery cover After seal, obtain button gel polymer lithium ion battery；
The electrolyte is with LiPF6It is 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 resins solution is prepared by following methods：In mass ratio For 5: 95 by the proton type perfluor sulfoacid resin solution (95g) of polyethylene glycol oxide (PEO, 5g) addition mass concentration 5wt%, stir Nafion-PEO blending resin solution is obtained after mixing dissolving.
In the present invention, the barrier film is prepared by following methods：Nafion-PEO blending resin solution is fallen In horizontal glass plate, after solvent evaporates, the barrier film of the 0.05mm thickness of formation.
In the present invention, the NaCl-KCl eutectic salts are prepared by following methods：In mass ratio 45:55 will NaCl and KCl added ball grinder, with rotating speed 700rpm ball millings 1 hour；Then heated 2 hours at 700 DEG C, be cooled to 25 DEG C, obtained To NaCl-KCl eutectic salts.
Inventive principle is described：
The present invention as obtained in butyl titanate and lithium acetate lithium titanate precursor gel and glucose, melamine, NaCl-KCl eutectic salts are uniformly mixed, and by after calcining, salinity being washed with deionized water, obtain 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 mixings, by after calcining, salinity being washed with water, obtain Graphene and support nanometer boron as the negative of battery Pole material, using the blend of type lithium ion perfluorinated sulfonic resin and polyethylene glycol oxide for base absorbs lithium-ion battery electrolytes 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 Changes are quite big before and after the embedding lithium of boron during discharge and recharge, and Graphene possesses intensity and flexibility very high, available buffer The Volume Changes of the embedding lithium of boron, so as to reduce the influence to electrode structure.
Negative pole of the invention supports a nanometer boron using Graphene, in the nafion-PEO blending resins and both positive and negative polarity of barrier film Blending resin combines together, forms 3-dimensional contiguous network.In subsequent electrolyte dipping process, electrolyte is distributed along three-dimensional network To electrode graphene layer between, formed liquid film；There is lithium ion exchanged simultaneously so that proton type perfluorosulfonic acid resin (nafion) turns Chemical conversion type lithium ion perfluorinated sulfonic resin.During charging there is Li in positive pole4Ti5O12De- lithium process, lithium ion along three-dimensional network pass It is defeated that the process of intercalation of boron occurs to negative pole, form boron lithium alloy.The mobile reverse of lithium ion during electric discharge, the lithium deintercalation in boron lithium, Lithium ion is transferred to positive pole along three-dimensional network, forms Li4Ti5O12。
Nanometer Li4Ti5O12With boron be in-situ preparation on nitrogenous Graphene, with activity very high, nitrogenous Graphene with There is B-N keys between boron so that boron particulate is securely seated between on Graphene.Graphene has electric conductivity very high, can be effective Improve Li4Ti5O12Electric conductivity.Graphene also possesses intensity and flexibility very high, therefore can effectively be absorbed during discharge and recharge The Volume Changes that the embedding lithium of boron is brought.Nitrogen in nitrogenous Graphene contains lone pair electrons as nucleophilic center, is beneficial to during discharge and recharge Electrolyte liquid film of the Li ions between graphene layer is uniformly distributed, so that greatly reduce the ohmage of both positive and negative polarity, so as to carry 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 generation glucose- Melmac and water, Li4Ti5O12Colloidal sol is dehydrated to form unformed Li4Ti5O12；When being warming up to 440 DEG C and preparing positive electrode During, glucose-urea resin takes place carbonization；Li4Ti5O12Structure be changed into spinel structure by unformed； Glucose-the melmac of preliminary carbonization is coated on eutectic salts and spinel structure in 440 DEG C of insulating processes Li4Ti5O12On the particulate of composition.800 DEG C are warming up to, carbonization after heating 2 hours is cooled to room temperature and obtains saliferous Graphene Support a nanometer Li4Ti5O12；When glucose-melmac is carbonized, due to eutectic salts and nanometer Li4Ti5O12Space Blocking effect, glucose-melmac is carbonized to form graphene-structured；
In the present invention, in negative material preparation process, the glucose-trimerization of preliminary carbonization during 440 DEG C is warming up to Melamine resin is coated on the particulate 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, room temperature is cooled to and is obtained saliferous Graphene and support a nanometer boron；
In the present invention, membrane electrode when being heat-treated for 140 DEG C, being total in the nafion-PEO blending resins of barrier film and both positive and negative polarity Mixed resin combines together, forms 3-dimensional contiguous network.In subsequent electrolyte dipping process, electrolyte is distributed to along three-dimensional network Between the graphene layer of electrode, and adsorbed by Graphene, form liquid film；There is lithium ion exchanged simultaneously so that proton type fluosulfonic acid Resin (nafion) changes into type lithium ion perfluorinated sulfonic resin.
Compared with prior art, the device have the advantages that：
Graphene of the invention supports a nanometer boron lithium has good chemical stability, and boron has high storage lithium specific capacity Characteristic, barrier film of the invention is Nafion-PEO blending resins, the ability with Electolyte-absorptive very high, with lithium very high Ionic conductivity；Nanometer Li4Ti5O12With boron be in-situ preparation on nitrogenous Graphene, with activity very high, form a kind of Gel polymer lithium ion battery.Due in the absence of free state electrolyte, significantly improving the security of lithium ion battery, containing The nanometer boron and Li formed between nitrogen graphene layer4Ti5O12, be conducive to the stabilization of electrode structure, the good electric conductivity of Graphene to have Beneficial to heavy-current discharge, for electric automobile provides safe and reliable high-energy power battery.
Brief description of the drawings
Fig. 1 supports a nanometer Li for Graphene4Ti5O12Transmission electron microscope photo.
Fig. 2 is the gel polymer lithium ion battery of preparation in embodiment seven in 25 DEG C, the cyclic voltammetric of 0.2C speed Curve, sets specific capacity as the theoretical embedding lithium capacity of boron：C=3100mAh/g.
Reference in Fig. 2 is：
1 discharge curve, 2 charging curves.
Specific embodiment
Present invention will be described in detail below.
Embodiment one：The preparation of NaCl-KCl eutectic salts
NaCl (45g) and KCl (55g) is added into ball grinder, ball milling 1 hour under rotating speed 700rpm, taking-up is put into crucible, empty 700 DEG C are heated 2 hours in gas, are cooled to 25 DEG C, obtain NaCl-KCl eutectic salts.
Embodiment two：Graphene supports the preparation of nanometer boron
Obtained NaCl-KCl eutectic salts (30g) in Example one, in mass ratio 4 in ball grinder:2:1:300 add Single water glucose, melamine, metaboric acid and NaCl-KCl eutectic salts, rotating speed 700rpm ball milling mixings 2 hours are obtained Graphene Support a nanometer presoma for boron lithium；
Be warming up under nitrogen atmosphere 110 DEG C heating 2 hours after, be warming up to after vacuumizing 440 DEG C insulation 8 hours after, heat up Heated 2 hours to 900 DEG C, three times programming rate is 10 DEG C/min, is subsequently cooled to room temperature, obtains saliferous Graphene and supports nanometer Boron.It is vacuum dried after washing salinity with deionized water, obtains Graphene and support a nanometer boron.
Embodiment three：Nafion-PEO blending resins solution is modulated
5g is added in the proton type perfluor sulfoacid resin solution of the mass content 5wt% of 95g du pont company production PEO (polyethylene glycol oxide), obtains Nafion-PEO blending resin solution after stirring and dissolving.
Example IV：It is prepared by barrier film
The Nafion-PEO blending resin solution that will be obtained in embodiment three, is poured in horizontal glass plate, after solvent evaporation The 0.05mm of formation thick Nafion-PEO blending resin films.
Embodiment five：The preparation of negative pole
Obtained Graphene is modulated in supporting a nanometer boron (0.8g), acetylene black (0.1g) and embodiment three in Example two Nafion-PEO blending resins solution (1g), Graphene is supported into nanometer boron lithium alloy, acetylene black, a Nafion solution, by matter Amount compares 80: 10: 100 mixed grindings, is coated in city's dealer's nickel foam after being modulated into paste；In 100Kg/cm after drying in the shade2Pressure Under it is compressing, obtain negative pole.
Embodiment six：Li4Ti5O12The preparation of colloidal sol
Sequentially add 30 grams of citric acids and 34 grams of butyl titanate in 300 milliliters of ethanol, ultrasonic disperse 40 minutes, Form solution A；During 50 grams of citric acids are added into 60 milliliters of ethanol, then it is added thereto to 30 ml deionized waters and 5.28 grams of second Sour lithium forms B solution.By solution A after 30 DEG C of temperature constant magnetic stirrings 30 minutes, B solution is added dropwise in solution A, obtained Colloidal sol；10 grams of citric acids are added in colloidal sol makes the pH value of colloidal sol be 1.2, persistently stirs 1 hour, obtains precursor sol.
Embodiment seven：Graphene supports a nanometer Li4Ti5O12Preparation
The precursor sol obtained in embodiment six adds the mono- water glucose of 40g, 20g melamines and 300g NaCl- KCl eutectic salts, stir into pasty state, and prepared Graphene supports a nanometer Li4Ti5O12Presoma；110 DEG C are warming up under nitrogen atmosphere Heating 2 hours after, be warming up to after vacuumizing 440 DEG C insulation 8 hours after, be warming up to 800 DEG C heat 2 hours, three programming rates It is 10 DEG C/min, is subsequently cooled to room temperature and obtains saliferous Graphene to support a nanometer Li4Ti5O12.Salinity is washed with deionized water After be vacuum dried, obtain Graphene and support a nanometer Li4Ti5O12。
Embodiment eight：The preparation of positive pole
Graphene prepared by Example seven supports a nanometer Li4Ti5O12(0.8g), acetylene black (0.1g), embodiment three are made Standby Nafion-PEO blending resins solution (1g), a nanometer Li is supported by Graphene4Ti5O12, acetylene black, Nafion-PEO blending 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 it is compressing, obtain positive pole.
Embodiment nine：The assembling of button gel polymer lithium ion battery
The positive pole (taking the disk of a diameter of 18mm) that will be obtained in embodiment eight, the barrier film (diameter prepared in example IV It is 19mm) it is placed on positive pole；The negative pole (taking the disk of a diameter of 18mm) obtained in embodiment three is placed on barrier film； 100Kg/cm2Under pressure it is compressing after, in blanket of nitrogen, 140 DEG C of heat treatments obtain membrane electrode in 2 hours, in electrolyte after cooling Middle dipping obtains battery core in 2 hours.The positive pole of battery core is placed in city dealer's button cell shell (CR2025), is connect with battery case Touch；After a diameter of 18mm, thickness 1mm, the foam nickel sheet that voidage is 98% on the negative side pad of battery core, 0.5mL electrolysis are added Liquid, seals after encryption seal and battery cover, obtains button gel polymer lithium ion battery.Electrolyte is with LiPF6It is 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, in one liter of electrolyte contain 151.9 grams of lithium hexafluoro phosphates.
Embodiment ten：The charge and discharge of gel polymer lithium ion battery
When the gel polymer lithium ion battery obtained in embodiment nine charges, there is Li in positive pole4Ti5O12De- lithium mistake There is process of intercalation in journey, the boron of negative pole, when the embedding full lithium of boron, charge cutoff.
During electric discharge, there is process of intercalation in positive pole, and there is the deintercalation of lithium in the boron lithium of negative pole, when the lithium in boron lithium is all de- It is embedding, electric discharge cut-off.Fig. 2 is gel polymer lithium ion battery in 25 DEG C, the cyclic voltammetry curve of 0.2C speed, setting specific volume Measure the theoretical embedding lithium capacity for boron：C=3100mAh/g
Finally, in addition it is also necessary to it is noted that listed above is only specific embodiment of the invention.Obviously, the present invention is not limited In above example, there can also be many deformations.One of ordinary skill in the art can directly lead from present disclosure The all deformations for going out or associating, are considered as protection scope of the present invention.

Claims (6)

1. the preparation method of the positive electrode of gel polymer lithium ion battery is used for, it is characterised in that the positive electrode is Graphene supports a nanometer Li4Ti5O12, its preparation comprises the following steps：
(1) 30 grams of citric acids and 34 grams of butyl titanate are sequentially added in 300 milliliters of ethanol, ultrasonic disperse 40 minutes, Form solution A；
(2) in 50 grams of citric acids being added into 60 milliliters of ethanol, then 30 ml deionized waters and 5.28 grams of acetic acid are added thereto to Lithium forms B solution；
(3) is added dropwise to B solution in solution A after 30 DEG C of temperature constant magnetic stirrings 30 minutes by solution A, obtains colloidal sol；
(4) make the pH value of colloidal sol be 1.2 to 10 grams of citric acids of addition in step (3) gained colloidal sol, persistently stir 1 hour, obtain Precursor sol；
(5) to the mono- water glucose of 40g, 20g melamines and 300g NaCl-KCl eutectic salts are added in precursor sol, stir Into pasty state, prepared Graphene supports a nanometer Li4Ti5O12Presoma；
(6) presoma that will be obtained be warming up under nitrogen atmosphere 110 DEG C heating 2 hours after, 440 DEG C of insulations are warming up to after vacuumizing 8 hours, it is warming up to 800 DEG C and heats 2 hours, three times programming rate is 10 DEG C/min；Room temperature is subsequently cooled to, saliferous stone is obtained Black alkene supports a nanometer Li4Ti5O12；
(7) saliferous Graphene is supported into a nanometer Li4Ti5O12Salinity is washed with deionized water, after vacuum drying, Graphene is obtained Support a nanometer Li4Ti5O12。
2. the Graphene for being obtained using claim 1 methods described supports a nanometer Li4Ti5O12Prepare gel polymer lithium ion The method of the positive pole of battery, it is characterised in that including step：
(1) in mass ratio 80: 10: 100 take Graphene and support a nanometer Li4Ti5O12, acetylene black, Nafion-PEO blending resins it is molten Liquid；
(2) Graphene is supported into a nanometer Li4Ti5O12, acetylene black, Nafion-PEO blending resins solution mixing, grinding, be modulated into It is coated in nickel foam after paste；In 100Kg/cm after drying in the shade2Pressure under it is compressing, obtain positive pole.
3. the method that the positive pole for being obtained using claim 3 methods described prepares gel polymer lithium ion battery, its feature It is to comprise the steps：
(1) the single water glucose of in mass ratio 4: 2: 1: 300 additions, melamine, metaboric acid and NaCl-KCl are common in ball grinder Brilliant salt, with rotating speed 700rpm ball milling mixings 2 hours, prepared Graphene supported the presoma of nanometer boron；
(2) presoma that will be obtained be warming up under nitrogen atmosphere 110 DEG C heating 2 hours after, 440 DEG C of insulations are warming up to after vacuumizing After 8 hours, it is warming up to 900 DEG C and heats 2 hours, three programming rates is 10 DEG C/min；Room temperature is subsequently cooled to, saliferous stone is obtained Black alkene supports a nanometer boron；
(3) saliferous Graphene is supported into a nanometer boron deionized water and washes salinity, after vacuum drying, obtain Graphene and support to receive Rice boron；
(4) in mass ratio 80: 10: 100 take Graphene and support a nanometer boron, acetylene black, Nafion-PEO blending resin solution, mix Grinding, is coated in nickel foam after being modulated into paste；In 100Kg/cm after drying in the shade2Pressure under it is compressing, obtain negative pole；
(5) arranged by the order of positive pole, barrier film, negative pole, in 100Kg/cm2Under pressure it is compressing after, in blanket of nitrogen and 140 DEG C Heat treatment obtains membrane electrode in 2 hours, is impregnated in the electrolytic solution after cooling 2 hours and obtains battery core；
(6) positive pole 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 Footpath is close after encryption seal and battery cover after 18mm, thickness 1mm, the foam nickel sheet that voidage is 98%, to add 0.5mL electrolyte Envelope, obtains button gel polymer lithium ion battery；
The electrolyte is with LiPF6It is 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, it is characterised in that the Nafion-PEO blending resins solution is to pass through What following methods were prepared：Add the proton type of mass concentration 5wt% full peo resin for 5: 95 in mass ratio Nafion-PEO blending resin solution is obtained in perfluorosulfonic acid resin solution, after stirring and dissolving.
5. method according to claim 3, it is characterised in that the barrier film is prepared by following methods：Will Nafion-PEO blending resin solution is poured in horizontal glass plate, after solvent evaporates, the barrier film of the 0.05mm thickness of formation.
6. the method according to claims 1 to 3 any one, it is characterised in that the NaCl-KCl eutectic salts are logical Cross what following methods were prepared：In mass ratio 45:NaCl and KCl is added ball grinder by 55, small with rotating speed 700rpm ball millings 1 When；Then heated 2 hours at 700 DEG C, be cooled to 25 DEG C, obtain NaCl-KCl eutectic salts.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108281300A (en) * 2017-12-29 2018-07-13 华南师范大学 A kind of preparation method of the nitrogen-doped titanic acid lithium micro-nano-sphere of graphene coated
CN109638295A (en) * 2018-11-02 2019-04-16 浙江大学 The preparation method of oxygen reduction catalyst based on metal organic framework compound
CN109802175A (en) * 2019-01-22 2019-05-24 常州天宇宏图电子有限公司 A kind of preparation method of sodium-ion battery gel state electrolyte

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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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Publication number Priority date Publication date Assignee Title
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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Publication number Priority date Publication date Assignee Title
CN108281300A (en) * 2017-12-29 2018-07-13 华南师范大学 A kind of preparation method of the nitrogen-doped titanic acid lithium micro-nano-sphere of graphene coated
CN109638295A (en) * 2018-11-02 2019-04-16 浙江大学 The preparation method of oxygen reduction catalyst based on metal organic framework compound
CN109638295B (en) * 2018-11-02 2021-06-04 浙江大学 Preparation method of oxygen reduction catalyst based on metal organic framework compound
CN109802175A (en) * 2019-01-22 2019-05-24 常州天宇宏图电子有限公司 A kind of preparation method of sodium-ion battery gel state electrolyte

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