CN104681804B - A kind of carbon-coated nano lithium titanate composite material and its preparation method and application - Google Patents

A kind of carbon-coated nano lithium titanate composite material and its preparation method and application Download PDF

Info

Publication number
CN104681804B
CN104681804B CN201510055410.0A CN201510055410A CN104681804B CN 104681804 B CN104681804 B CN 104681804B CN 201510055410 A CN201510055410 A CN 201510055410A CN 104681804 B CN104681804 B CN 104681804B
Authority
CN
China
Prior art keywords
lithium titanate
carbon
lithium
source
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510055410.0A
Other languages
Chinese (zh)
Other versions
CN104681804A (en
Inventor
舒东
康宗轩
邹献平
廖雨清
郝俊楠
钟雅云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China Normal University
Original Assignee
South China Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China Normal University filed Critical South China Normal University
Priority to CN201510055410.0A priority Critical patent/CN104681804B/en
Publication of CN104681804A publication Critical patent/CN104681804A/en
Application granted granted Critical
Publication of CN104681804B publication Critical patent/CN104681804B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of carbon-coated nano lithium titanate composite material and preparation method thereof.Methods described includes：S1. the preparation of nano lithium titanate：Lithium source, titanium source microemulsion are prepared respectively, two kinds of microemulsions are mixed, is stood, and centrifugation, are carried out alternately washing with organic solvent and water, are dried, high-temperature calcination；S2. the carbon coating of nano lithium titanate：Solution is made in organic carbon source, the lithium titanate particle that S1 is prepared then is added, ultrasonic disperse, hydro-thermal reaction, carries out alternately washing with organic solvent and water after reaction cooling, filtering, carbon-coated nano lithium titanate composite material is obtained after drying.The present invention realizes the refinement of lithium titanate using micro emulsion method, and solution is made in carbon source, the carbon coating of nanoscale lithium titanate is realized using hydro-thermal reaction, uniform, compact conductive carbon network is formed on lithium titanate surface, the electric conductivity of electrode material and high-power charge-discharge performance are significantly improved, available for preparing lithium-ion capacitor and lithium ion battery.

Description

A kind of carbon-coated nano lithium titanate composite material and its preparation method and application
Technical field
The invention belongs to electrode material technical field, in particular it relates to a kind of carbon-coated nano lithium titanate composite material and Its preparation method and application.
Background technology
Due to energy and environment problem getting worse, the exploitation of clean energy resource is extremely urgent with using.With electronic technology Make rapid progress, electronic apparatus constantly towards miniaturization and high performance direction fast development.Especially mobile communication, notes The extensive use of the portable electronic equipment such as this computer and video camera, higher requirement is proposed to high-performance energy storage device, is made There must be high power density lithium-ion capacitor to obtain unprecedented development.
Lithium-ion capacitor is a kind of energy storage device based on ultracapacitor and the dual energy storage mechanism of lithium ion battery, just Pole uses the material with super capacitor performance, such as activated carbon, and negative pole uses Lithium-ion embeding abjectionization material, has energy close Degree and power density are high, long lifespan and it is safe the features such as, be expected to be applied to pure EHV electric and hybrid vehicle field.Lithium Negative material used in ionistor is generally graphite, but its energy storage potential plateau is relatively low, in 0~0.25V vs Li/ Li+Between, the generation of Li dendrite is frequently can lead to, which greatly limits graphite answering in lithium-ion capacitor With.With graphite-phase ratio, lithium titanate has very big advantage, is mainly manifested in, deintercalation of the lithium ion in lithium titanate be it is reversible, And lithium ion is during embedded and abjection lithium titanate, and its crystal formation does not change, and Volume Changes are less than 1%, therefore again It is referred to as " zero strain material ".Due to " zero strain " property of lithium titanate, can avoid in charge and discharge cycles due to electrode material Material stretches and causes structural damage back and forth, so as to improve the cycle performance of electrode and service life.But due to lithium titanate Electrical conductivity it is low, cause the high-power performance of material relatively low, when being worked under high power environment, lithium titanate special capacity fade is fast Speed.
At present, to improve electric conductivity, the method mainly used is the refinement of lithium titanate particle, or lithium titanate and electric conductivity The materials such as excellent metal, carbon and polymer carry out compound.The refinement main method of lithium titanate particle have mechanical lapping, hydro-thermal, Collosol and gel and micro emulsion method etc., wherein micro emulsion method are by controlling the proportioning of each material in microemulsion, so as to effectively control metatitanic acid The size of lithium particle, the lithium titanate particle of preparation is set to reach nanoscale.But during lithium titanate preparation in solid-phase sintering process Particle easily grows, reunited seriously, is unfavorable for the preparation of nanoscale lithium titanate.Compound method mainly has mechanical mixture, high temperature There is operating time length in calcining and cladding, wherein mechanical mixing, mixing is uneven, it is difficult to controls the surface configuration and grain of product The reunion of particle and needs under calcining heat high (500~800 DEG C), hot conditions be present in the shortcomings of sub- size, high-temperature calcination The shortcomings of inert gas shielding, compared with mechanical mixture and high-temperature calcination, it is most that the carbon of lithium titanate and good conductivity, which carries out cladding, Widespread practice.But existing carbon coating method is present that the operating time is long, cladding is uneven, with reference to not close, calcining heat Height, the problems such as inert gas shielding is needed, be unfavorable for the utilization of carbon coating lithium titanate particle.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of preparation side of carbon-coated nano lithium titanate composite material Method.The present invention realizes the refinement of lithium titanate using micro emulsion method, and carbon source is made into solution, and nano grade titanium is realized using hydro-thermal reaction The carbon coating of sour lithium, uniform, compact conductive carbon network is formed on lithium titanate surface, significantly improves leading for electrode material Electrical and high-power charge-discharge performance.
The carbon-coated nano lithium titanate composite material being prepared another object of the present invention is to provide the above method.
Another object of the present invention is to provide above-mentioned composite in lithium-ion capacitor and lithium ion battery is prepared Application.
The above-mentioned purpose of the present invention is achieved by the following technical programs.
A kind of preparation method of carbon-coated nano lithium titanate composite material, comprises the following steps：
S1. the preparation of nano lithium titanate：Oil phase, surfactant and cosurfactant are mixed to get microemulsion, will Lithium source, titanium source are separately added into microemulsion, prepare lithium source microemulsion and titanium source microemulsion, and two kinds of microemulsions are mixed, stirred, Stand, centrifugation, take precipitation to carry out alternately washing with organic solvent and water, dry, lithium titanate particle is obtained after high-temperature calcination；
S2. the carbon coating of nano lithium titanate：Solution is made in organic carbon source, then adds the nano-titanium that S1 is prepared Sour lithium particle, ultrasonic disperse；Obtained mixture is subjected to hydro-thermal reaction under elevated pressure conditions, after reaction cooling, takes out product, Alternately washing is carried out with organic solvent and water, filtering, carbon-coated nano lithium titanate composite material is obtained after drying.
The present invention prepares lithium titanate using micro emulsion method, and nanoscale lithium titanate particle is prepared, has larger ratio surface Product, improve the high rate charge-discharge performance of lithium titanate；And during carbon coating, solution is made in carbon source, beneficial to uniform Ground is covered in the surface of lithium titanate, and after hydro-thermal method carbonization, uniform, compact conductive carbon network is formed on lithium titanate surface, Be advantageous to improve the electric conductivity of electrode material, after lithium titanate coated with carbon, high-power charge-discharge performance is significantly improved； During carrying out carbon coating using hydro-thermal reaction, reaction temperature is relatively low, it is possible to prevente effectively from nano lithium titanate is in high-temperature calcination During the agglomeration that occurs, keep high-ratio surface, the conductance of material improved, so as to improve the high-power property of composite Energy.
Preferably, the concentration of the titanium source is 20mmol/L~1mol/L, the concentration of the lithium source for 17mmol/L~ 1mol/L。
Preferably, the temperature dried described in S1 is 50~100 DEG C, and the time is 2~20h, and vacuum is 0.1~101kPa.
Preferably, the temperature of high-temperature calcination described in S1 is 500~800 DEG C, and the time is 6~15h.
Preferably, the concentration of organic carbon source described in S2 is 10~300g/L.
Preferably, the temperature of hydro-thermal reaction described in S2 is 100~280 DEG C, and the reaction time be 3~20h, reaction pH for 8~ 13.It is highly preferred that the temperature of hydro-thermal reaction described in S2 is 110 ~ 230 DEG C.
Preferably, the temperature dried described in S2 is 20~100 DEG C, and the time is 0.5~8h, and vacuum is 0.1~101kPa.
Preferably, the content of carbon is 2%~20% in the carbon-coated nano lithium titanate composite material that S2 is prepared.
Preferably, the ultrasonic disperse time described in S2 is 0.5 ~ 40h.
It is highly preferred that described preparation method comprises the following steps：
S1. the preparation of nano lithium titanate：Oil phase, surfactant and cosurfactant are well mixed and obtain micro emulsion Liquid；Take 50mmol/L ~ 0.55mol/L titanium sources add microemulsion in, stirring 2h prepare titanium source microemulsion, take 42 mmol/L ~ 0.46mol/L lithium sources are added in microemulsion, and stirring 1h prepares lithium source microemulsion, and titanium source microemulsion and lithium source microemulsion are mixed, 3h is stirred, 24h is stood, centrifugation, takes precipitation to carry out alternately washing several times with organic solvent and water, at 65 ~ 80 DEG C, vacuum is Under conditions of 0.1 ~ 1kPa, 10 ~ 20h is dried, then 6 ~ 15h is calcined at 500 ~ 800 DEG C, nano lithium titanate is obtained after natural cooling Particle；
S2. the carbon coating of nano lithium titanate：The solution that concentration is 100~150g/L is made in organic carbon source, adds S1 systems Standby obtained nano lithium titanate particle, ultrasonic disperse 1h；Obtained mixture is moved into hydrothermal reaction kettle, controls pH 9 ~ 11, 150 ~ 180 DEG C of 5 ~ 12h of reaction, after product takes out, carry out alternately washing several times with organic solvent and water, filtering, 65 ~ 80 DEG C true Sky dries 5 ~ 8h, and vacuum is 0.5 ~ 1kPa, obtains carbon-coated nano lithium titanate composite material.
Preferably, oil phase described in S1 is the one or more in hexamethylene, toluene, oleic acid or dichloromethane.
Preferably, surfactant described in S1 is Triton X-100（Triton X -100）, cetyl three Methyl bromide ammonium（CTAB）, OPEO（OP）, cetyl polyoxy hexenyl ether or neopelex In one or more.
Preferably, cosurfactant described in S1 is n-butanol.
Preferably, titanium source described in S1 is in Titanium Nitrate, tetraethyl titanate, metatitanic acid methyl esters, isopropyl titanate or iso-butyl titanate One or more.
Preferably, lithium source described in S1 is one kind or more in lithium chloride, lithium acetate, lithium nitrate, lithium sulfate or lithium hydroxide Kind.
Preferably, organic solvent described in S1 is the one or more in acetone, methanol, ethanol or carbon tetrachloride, described in S2 Organic solvent is the one or more in acetone, methanol, DMSO or butanol.
Preferably, titanium source microemulsion described in S1 and lithium source microemulsion hybrid mode are quick mixing.
Preferably, organic carbon source described in S2 is the one or more in maltose, fructose, lactose or starch, it is highly preferred that Organic carbon source described in S2 is maltose or/and starch.
Preferably, the dispersant for disperseing organic carbon source described in S2 is water or ethanol.
The carbon-coated nano lithium titanate composite material that a kind of above method is prepared.
A kind of application of above-mentioned composite in lithium-ion capacitor and lithium ion battery is prepared.
Compared with prior art, the beneficial effects of the present invention are：
（1）The present invention using micro emulsion method prepares lithium titanate, and the lithium titanate particle being prepared is in nanoscale, with larger Specific surface area, improve the high rate charge-discharge performance of lithium titanate；Solution is made in carbon source by the present invention, beneficial to being equably covered in The surface of lithium titanate, after hydro-thermal method carbonization, uniform, compact conductive carbon network is formed on lithium titanate surface, is advantageous to carry The electric conductivity of high composite, after lithium titanate coated with carbon, high-power charge-discharge performance is significantly improved.
（2）The present invention is during carbon coating, and the reaction temperature of hydro-thermal reaction is relatively low, it is possible to prevente effectively from nano lithium titanate The agglomeration occurred in high-temperature burning process, high-ratio surface is kept, the conductance of material is improved, so as to improve composite High-power performance.
（3）The particle diameter of lithium titanate particulate is nanoscale, ensure that lithium titanate composite material in charge and discharge process, lithium ion The distance of diffusion is shorter, greatly increases the diffusion rate of lithium ion, it is achieved thereby that lithium titanate composite material of the present invention quickly fills Discharge performance greatly improves.
（4）The preparation technology of the composite of the present invention is simple, and cost is low, easily realizes industrialized production；Electricity of the invention In the material preparation process of pole, produced without poisonous and hazardous material, meet the requirement of environmental protection.
Brief description of the drawings
Fig. 1 is the XRD analysis of nano lithium titanate particle prepared by the embodiment of the present invention 1.
Fig. 2 is the pore-size distribution of nano lithium titanate particle prepared by the embodiment of the present invention 1.
Embodiment
The present invention is described in further details with reference to Figure of description and specific embodiment, but embodiment is not right The present invention limits in any form.Unless stated otherwise, reagent, the method and apparatus that the present invention uses are normal for the art Advise reagent, method and apparatus.
Embodiment 1
0.67L Triton-100,0.4L n-butanols and 1.1L hexamethylenes are taken, is stirred, it is well mixed to obtain microemulsion, add Enter 0.5L, 0.2mol/L metatitanic acid methyl esters, stirring 2h prepares titanium source microemulsion；Take 0.67L Triton-100,0.4L n-butanols and 1.1L hexamethylenes, stirring is well mixed to obtain microemulsion, adds 0.5L, 0.17mol/L LiNO31h is stirred, it is micro- to form lithium source Emulsion, titanium source microemulsion and lithium source microemulsion are quickly mixed, stir 3h, stood 24h, centrifugation, precipitation second alcohol and water is entered Row alternately washing 4 times, at 65 DEG C, under conditions of vacuum is 0.1kPa, 16h is dried, obtains the presoma of lithium titanate, presoma Calcine 15h at 500 DEG C, after natural cooling, obtain the nanoparticle of lithium titanate, the XRD analysis of nano lithium titanate particle and hole Footpath distribution results are shown in Fig. 1, Fig. 2 respectively；0.1L, 130g/L starch solution are prepared, the above-mentioned systems of 88g are then added into the solution Standby nanoscale lithium titanate particle, ultrasonic disperse 1h, the mixture is moved into hydrothermal reaction kettle, control pH as 11,150 DEG C of reactions 12h, product use butanol and deionized water alternating washed product 3 times, 68 DEG C of vacuum drying 7h, vacuum 0.5kPa after taking out, Obtain carbon-coated nano lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material being prepared as electrode active material, according to electrode activity material Material：Carbon black：PVDF=85:10:5, add NMP to size mixing, upper electrode material is applied on aluminium foil with coating machine, thickness is at 125 μm, 100 DEG C drying, makes NMP volatilize, its thickness under argon atmosphere, is assembled at 70 ~ 90 μm in glove box with roll squeezer jewelling paper tinsel Asymmetric capacitor, activated carbon is as positive pole and uses excessive positive electrode, 1.5mol/L LiBF4As electrolyte, carry out permanent Charge-discharge test is flowed, when charging and discharging currents density is 0.5A/g（Calculated on the basis of negative pole）When, the ratio of lithium titanate composite material Capacity reaches 100F/g, and the composite materials for showing to prepare have preferable capacitive property；When charging and discharging currents density is 2.5A/ G, during circulation 5000 times, for capability retention 92%, the compound for showing to prepare has excellent electrochemistry cycle performance.
Embodiment 2
200g CTAB, 8L n-butanols and 22L toluene are taken, is stirred, it is well mixed to obtain microemulsion, add 1L, 0.5mol/L Metatitanic acid methyl esters, stirring 2h prepare titanium source microemulsion；200g CTAB, 8L n-butanols and 22L toluene are taken, is stirred, it is well mixed to obtain Microemulsion, add 1L, 0.42mol/L LiNO31h is stirred, forms lithium source microemulsion, titanium source microemulsion and lithium source microemulsion is fast Speed mixing, stirs 3h, stands 24h, centrifugation, carries out alternately washing 3 times with second alcohol and water to precipitation, at 73 DEG C, vacuum is Under conditions of 0.5kPa, 20h is dried, obtains the presoma of lithium titanate, presoma calcines 8h at 650 DEG C, after natural cooling, obtains To the nanoparticle of lithium titanate.0.1L, 140g/L starch solution are prepared, the above-mentioned preparations of 71g are then added into the solution Nano lithium titanate particle, ultrasonic disperse 1h, the mixture is moved into hydrothermal reaction kettle, 9,180 DEG C of reaction 8h of pH, product takes out Replace washed product 4 times with butanol and deionized water afterwards, 78 DEG C of vacuum drying 5h, vacuum 1kPa, obtain carbon-coated nano Lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material being prepared as electrode active material, according to electrode activity material Material：Carbon black：PVDF=85:10:5, add NMP to size mixing, upper electrode material is applied on aluminium foil with coating machine, thickness is at 125 μm, 90 DEG C drying, makes NMP volatilize, its thickness under argon atmosphere, is assembled at 70 ~ 90 μm in glove box with roll squeezer jewelling paper tinsel Asymmetric capacitor, activated carbon is as positive pole and uses excessive positive electrode, 1.5 mol/L LiBF4As electrolyte, carry out Constant current charge-discharge test, when charging and discharging currents density is 0.7A/g（Calculated on the basis of negative pole）When, the specific capacity of composite Reach 88F/g, the composite materials for showing to prepare have preferable capacitive property；When charging and discharging currents density is 3A/g, circulation At 4000 times, for capability retention 89%, the compound for showing to prepare has excellent electrochemistry cycle performance.
Embodiment 3
18g cetyl polyoxy hexenyls ether, 0.8L n-butanols and 2.2L toluene are taken, is stirred, it is well mixed to obtain micro emulsion Liquid, adds 1.2L, 50mmol/L isopropyl titanate, and stirring 2h prepares titanium source microemulsion；Take 18g cetyl polyoxy hexenyls ether, 0.8L n-butanols and 2.2L toluene, stirring is well mixed to obtain microemulsion, adds 1.2L, 42mmol/L LiCl stirring 1h, shape Into lithium source microemulsion, titanium source microemulsion and lithium source microemulsion are quickly mixed, stir 3h, stands 24h, centrifugation, to precipitation fourth Alcohol and water carries out alternately washing 3 times, at 81 DEG C, under conditions of vacuum is 1kPa, dries 10h, obtains the presoma of lithium titanate, Presoma calcines 6h at 800 DEG C, after natural cooling, obtains the nanoparticle of lithium titanate.Prepare 0.1L, 100g/L maltose Solution, the nano lithium titanate particle of the above-mentioned preparations of 48g is then added into the solution, ultrasonic disperse 1h, the mixture is moved into Hydrothermal reaction kettle, 11,160 DEG C of reaction 5h of pH, product use acetone and deionized water alternating washed product 4 times, 76 DEG C after taking out 6h is dried in vacuo, vacuum 0.8kPa, obtains carbon-coated nano lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material being prepared as electrode active material, according to electrode activity material Material：Carbon black：PVDF=85:10:5, add NMP to size mixing, upper electrode material is applied on aluminium foil with coating machine, thickness is at 125 μm, 100 DEG C drying, makes NMP volatilize, its thickness under argon atmosphere, is assembled at 70 ~ 90 μm in glove box with roll squeezer jewelling paper tinsel Asymmetric capacitor, activated carbon is as positive pole and uses excessive positive electrode, 1.5 mol/L LiBF4As electrolyte, carry out Constant current charge-discharge test, when charging and discharging currents density is 1A/g（Calculated on the basis of negative pole）When, the specific capacity of composite reaches To 75F/g, the composite materials for showing to prepare have preferable capacitive property；When charging and discharging currents density is 3A/g, circulation At 5000 times, for capability retention 88%, the compound for showing to prepare has excellent electrochemistry cycle performance.
Embodiment 4
0.8L Triton-100,0.8L n-butanols and 2.2L oleic acid are taken, is stirred, it is well mixed to obtain microemulsion, add 1.2L, 0.45mol/L isopropyl titanate, stirring 2h prepare titanium source microemulsion；0.8L Triton-100,0.8L n-butanols and 2.2L Oleic acid, stirring is well mixed to obtain microemulsion, adds 1.2L, 0.38mol/L LiCl stirring 1h, forms lithium source microemulsion, titanium Source microemulsion and lithium source microemulsion quickly mix, and stir 3h, stand 24h, centrifugation, precipitation are replaced with carbon tetrachloride and water Washing 4 times, at 78 DEG C, under conditions of vacuum is 0.8kPa, 14h is dried, obtains the presoma of lithium titanate, presoma is 650 Calcine 10h at DEG C, after natural cooling, obtain the nanoparticle of lithium titanate.Prepare 0.1L, 150g/L starch solution, Ran Houxiang The nano lithium titanate particle of the above-mentioned preparations of 80g is added in the solution, ultrasonic disperse 1h, the mixture is moved into hydrothermal reaction kettle, PH is 10,180 DEG C of reaction 12h, and product uses DMSO and deionized water alternating washed product 3 times, 72 DEG C of vacuum drying 8h after taking out, Vacuum is 1kPa, obtains carbon-coated nano lithium titanate composite material.
Using the carbon-coated nano lithium titanate composite material being prepared as electrode active material, according to electrode activity material Material：Carbon black：PVDF=85:10:5, add NMP to size mixing, upper electrode material is applied on aluminium foil with coating machine, thickness is at 125 μm, 100 DEG C drying, makes NMP volatilize, its thickness under argon atmosphere, is assembled at 70 ~ 90 μm in glove box with roll squeezer jewelling paper tinsel Asymmetric capacitor, activated carbon is as positive pole and uses excessive positive electrode, 1.5 mol/L LiBF4As electrolyte, carry out Constant current charge-discharge test, when charging and discharging currents density is 0.8A/g（Calculated on the basis of negative pole）When, the specific capacity of composite Reach 83F/g, the composite materials for showing to prepare have preferable capacitive property；When charging and discharging currents density is 2A/g, circulation At 5000 times, for capability retention 90%, the compound for showing to prepare has excellent electrochemistry cycle performance.
Embodiment 5
16g neopelexes, 0.8L n-butanols and 2.2L oleic acid are taken, is stirred, it is well mixed to obtain microemulsion, add Enter 1.5L, 50mmol/L isopropyl titanate, stirring 2h prepares titanium source microemulsion；16g neopelexes, 0.8L n-butanols and 2.2L oleic acid, stirring is well mixed to obtain microemulsion, adds 1.5L, 42mmol/L LiNO31h is stirred, forms lithium source micro emulsion Liquid, titanium source microemulsion and lithium source microemulsion quickly mix, and stir 2h, stand 10h, centrifugation, precipitation carbon tetrachloride and water are entered Row alternately washing 4 times, at 62 DEG C, under conditions of vacuum is 0.6kPa, 15h is dried, obtains the presoma of lithium titanate, presoma Calcine 10h at 700 DEG C, after natural cooling, obtain the nanoparticle of lithium titanate.0.1L, 110g/L maltose solution are prepared, Then the nano lithium titanate particle of the above-mentioned preparations of 60g is added into the solution, ultrasonic disperse 1h, it is anti-that the mixture is moved into hydro-thermal Kettle, 10,130 DEG C of reaction 5h of pH are answered, product uses methanol and deionized water to replace washed product 4 times after taking out, 69 DEG C of vacuum are done Dry 8h, vacuum 1kPa, obtain carbon-coated nano lithium titanate composite material.
Embodiment 6
20gOP, 0.8L n-butanol and 2.2L toluene are taken, is stirred, it is well mixed to obtain microemulsion, add 1L, 0.2mol/L Metatitanic acid methyl esters, 2h is stirred, prepare titanium source microemulsion；20gOP, 0.8L n-butanol and 2.2L toluene, stirring, it is well mixed obtain it is micro- Emulsion；Add 1L, 0.17mol/L LiNO31h is stirred, forms lithium source microemulsion, titanium source microemulsion and lithium source microemulsion is quick Mixing, 3h is stirred, stand 24h, centrifugation, alternately washing 3 times are carried out with second alcohol and water to precipitation, at 63 DEG C, vacuum is Under conditions of 0.5kPa, 16h to be dried, obtains the presoma of lithium titanate, presoma calcines 12h at 600 DEG C, after natural cooling, Obtain the nanoparticle of lithium titanate.0.1L, 150g/L starch solution are prepared, the above-mentioned preparations of 68g are then added into the solution Nano lithium titanate particle, ultrasonic disperse 1h, the mixture is moved into hydrothermal reaction kettle, 8,190 DEG C of pH reaction 10h, product Replace washed product 4 times with butanol and deionized water after taking-up, 71 DEG C of vacuum drying 7h, vacuum 0.8kPa, obtain carbon bag Cover nano lithium titanate composite.
Comparative example 1
The method that this comparative example prepares carbon-coated nano lithium titanate composite material is substantially same as Example 1, except in S2 Organic carbon source is different from the hybrid mode of lithium titanate particle during carbon coating.This comparative example organic carbon source and lithium titanate particle Hybrid mode is：The nanoscale lithium titanate particle that starch solution and S1 are prepared is well mixed, added into 0.1L water, Ultrasonic disperse 1h.The carbon-coated nano lithium titanate composite material that this comparative example and embodiment 1 are obtained carries out constant current charge-discharge survey Examination, charging and discharging currents density and cycle-index are controlled respectively, compare the specific capacity and capability retention of both composites, as a result It is shown in Table 1.
Comparative example 2
The method that this comparative example prepares carbon-coated nano lithium titanate composite material is substantially same as Example 1, except this is right The method that ratio also uses high-temperature calcination after hydro-thermal reaction during S2 carbon coatings.The method of this comparative example carbon coating is：Will Mixture carries out 5~12h hydro-thermal reaction under conditions of pH 8~13,100~280 DEG C of temperature, then under reducing atmosphere 500~800 DEG C of 5~15h of calcining, obtain carbon-coated nano lithium titanate composite material.The carbon that this comparative example and embodiment 1 are obtained Coat nano lithium titanate composite and carry out constant current charge-discharge test, control charging and discharging currents density and cycle-index respectively, than Compared with the specific capacity and capability retention of both composites, 1 the results are shown in Table.
Comparative example 3
The preparation method of this comparative example S1 nano lithium titanates is same as Example 1, the carbon coating method of S2 nano lithium titanates It is different from embodiment 1.The method of this comparative example carbon coating is：The nanoscale lithium titanate particle that starch solution and S1 are prepared It is well mixed, add into 0.1L water, ultrasonic disperse 1h；The mixture is moved into hydrothermal reaction kettle, in pH 8~13, temperature 5~12h is reacted under conditions of 100~280 DEG C, reaction butanol and deionized water replace washed product 4 times, dry, are reducing 500~800 DEG C of 5~15h of calcining, obtain carbon-coated nano lithium titanate composite material under atmosphere.By this comparative example and embodiment 1 Obtained carbon-coated nano lithium titanate composite material carries out constant current charge-discharge test, controls charging and discharging currents density and circulation respectively Number, compare the specific capacity and capability retention of both composites, the results are shown in Table 1.
Influence of the 1 different preparation methods of table to composite property

Claims (9)

1. a kind of preparation method of carbon-coated nano lithium titanate composite material, it is characterised in that comprise the following steps：
S1. the preparation of nano lithium titanate：Oil phase, surfactant and cosurfactant are mixed to get microemulsion, by lithium Source, titanium source are separately added into microemulsion, prepare lithium source microemulsion and titanium source microemulsion, and two kinds of microemulsions are mixed, stirred, quiet Put, centrifuge, take precipitation to carry out alternately washing with organic solvent and water, dry, lithium titanate particle is obtained after high-temperature calcination；It is described to help Surfactant is n-butanol；The oil phase is the one or more in toluene, oleic acid or dichloromethane；The surfactant For the one or more in Triton X-100, OPEO or cetyl polyoxy hexenyl ether；Institute Titanium source is stated as the one or more in Titanium Nitrate, tetraethyl titanate, metatitanic acid methyl esters or iso-butyl titanate；High-temperature calcination described in S1 Temperature be 500~800 DEG C, the time is 6~15h；
S2. the carbon coating of nano lithium titanate：Solution is made in organic carbon source, then adds the nano lithium titanate that S1 is prepared Particle, ultrasonic disperse；Obtained mixture is subjected to hydro-thermal reaction under elevated pressure conditions, after reaction cooling, takes out product, with having Solvent and water carry out alternately washing, filtering, carbon-coated nano lithium titanate composite material are obtained after drying；The organic carbon source is One or more in maltose, fructose, lactose or starch.
2. preparation method according to claim 1, it is characterised in that the concentration of titanium source described in S1 be 20mmol/L~ 1mol/L, the concentration of the lithium source is 17mmol/L~1mol/L.
3. preparation method according to claim 1, it is characterised in that the temperature dried described in S1 is 50~100 DEG C, the time For 2~20h, vacuum is 0.1~101kPa.
4. preparation method according to claim 1, it is characterised in that the concentration of organic carbon source described in S2 is 10~300g/ L。
5. preparation method according to claim 1, it is characterised in that the temperature of hydro-thermal reaction described in S2 is 100~280 DEG C, the reaction time is 3~20h, and reaction pH is 8~13.
6. preparation method according to claim 1, it is characterised in that the temperature dried described in S2 is 20~100 DEG C, the time For 0.5~8h, vacuum is 0.1~101kPa.
7. preparation method according to claim 1, it is characterised in that the carbon-coated nano lithium titanate that S2 is prepared is compound The content of carbon is 2%~20% in material.
8. the carbon-coated nano lithium titanate composite material that any one of claim 1 ~ 7 methods described is prepared.
9. application of the composite described in claim 8 in lithium-ion capacitor and lithium ion battery is prepared.
CN201510055410.0A 2015-02-03 2015-02-03 A kind of carbon-coated nano lithium titanate composite material and its preparation method and application Active CN104681804B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510055410.0A CN104681804B (en) 2015-02-03 2015-02-03 A kind of carbon-coated nano lithium titanate composite material and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510055410.0A CN104681804B (en) 2015-02-03 2015-02-03 A kind of carbon-coated nano lithium titanate composite material and its preparation method and application

Publications (2)

Publication Number Publication Date
CN104681804A CN104681804A (en) 2015-06-03
CN104681804B true CN104681804B (en) 2018-03-30

Family

ID=53316584

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510055410.0A Active CN104681804B (en) 2015-02-03 2015-02-03 A kind of carbon-coated nano lithium titanate composite material and its preparation method and application

Country Status (1)

Country Link
CN (1) CN104681804B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328891B (en) * 2016-08-29 2019-02-12 深圳博磊达新能源科技有限公司 A kind of nano lithium titanate composite material and preparation method, lithium titanate battery
CN107275598B (en) * 2017-05-27 2020-02-14 广东烛光新能源科技有限公司 Lithium titanate negative electrode material and preparation method thereof
CN107482184A (en) * 2017-07-14 2017-12-15 东莞市迈科科技有限公司 A kind of preparation method of lithium titanate cathode of lithium ion battery composite
CN107808953B (en) * 2017-10-17 2020-05-22 合肥国轩高科动力能源有限公司 Preparation method of lithium titanate negative electrode material with low moisture absorption and less gas generation
CN107946554A (en) * 2017-10-26 2018-04-20 天津普兰能源科技有限公司 A kind of preparation method of lithium battery lithium titanate anode material
CN108232122A (en) * 2018-01-22 2018-06-29 南京大学射阳高新技术研究院 The preparation method and application of the lithium titanate nano particle of PEDOT claddings
CN108134072B (en) * 2018-01-30 2022-01-28 中国科学院宁波材料技术与工程研究所 Lithium titanate-based composite material and preparation method thereof
CN109037631A (en) * 2018-07-25 2018-12-18 国网新疆电力有限公司电力科学研究院 Carbon coating lithium titanate and preparation method thereof
CN110201659A (en) * 2019-05-14 2019-09-06 齐鲁理工学院 A kind of method of activated carbon supported Nano titanium dioxide
CN112885992A (en) * 2021-01-12 2021-06-01 厦门厦钨新能源材料股份有限公司 Preparation method and application of lithium ion battery negative electrode material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102315453A (en) * 2011-09-13 2012-01-11 清华大学深圳研究生院 Method for synthesizing lithium titanate electrode material
CN102544487A (en) * 2011-12-22 2012-07-04 浙江天能能源科技有限公司 Hydrothermal assisted micro-emulsion method for preparing nano-LiFePO4
CN103274454A (en) * 2013-05-19 2013-09-04 吉林大学 Hydrothermal synthesis method of micro-emulsion of nano lithium titanate
CN104282886A (en) * 2014-10-14 2015-01-14 江苏华东锂电技术研究院有限公司 Carbon coating method for electrode active material of lithium ion battery
CN104300120A (en) * 2014-09-17 2015-01-21 山东精工电子科技有限公司 Hydrothermal synthesis method of nano-lithium titanate material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101894943A (en) * 2010-04-20 2010-11-24 华南师范大学 Method for coating lithium ion battery anode material with carbon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102315453A (en) * 2011-09-13 2012-01-11 清华大学深圳研究生院 Method for synthesizing lithium titanate electrode material
CN102544487A (en) * 2011-12-22 2012-07-04 浙江天能能源科技有限公司 Hydrothermal assisted micro-emulsion method for preparing nano-LiFePO4
CN103274454A (en) * 2013-05-19 2013-09-04 吉林大学 Hydrothermal synthesis method of micro-emulsion of nano lithium titanate
CN104300120A (en) * 2014-09-17 2015-01-21 山东精工电子科技有限公司 Hydrothermal synthesis method of nano-lithium titanate material
CN104282886A (en) * 2014-10-14 2015-01-14 江苏华东锂电技术研究院有限公司 Carbon coating method for electrode active material of lithium ion battery

Also Published As

Publication number Publication date
CN104681804A (en) 2015-06-03

Similar Documents

Publication Publication Date Title
CN104681804B (en) A kind of carbon-coated nano lithium titanate composite material and its preparation method and application
CN107369825B (en) Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof
CN103972497B (en) Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof
CN102916195B (en) Graphene-coated copper oxide composite cathode material and method for manufacturing same
CN103682327B (en) Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel
CN104332630B (en) A kind of surface coated graphite cathode material and preparation method thereof and include its lithium ion battery
CN105883940B (en) Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery
CN105938899A (en) Preparation method and application of cathode material of fast ion conductor coated modified lithium ion battery
CN104852028A (en) Lithium titanate/graphene composite cathode material for lithium ion battery
CN104466102A (en) Porous V2O5/C composite microspheres of lithium secondary battery positive electrode material and preparation method of porous V2O5/C composite microspheres
CN107275571A (en) A kind of full battery of lithium sulfide/nano-silicone wire/carbon and preparation method and application
CN105789615A (en) Modified lithium nickel cobalt manganese cathode material and preparation method thereof
CN103762354A (en) LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery
Tian et al. Superimposed effect of La doping and structural engineering to achieve oxygen-deficient TiNb2O7 for ultrafast Li-ion storage
CN103682277B (en) Hollow porous nickel oxide composite material of N doping carbon-coating parcel and preparation method thereof
CN103151506A (en) Preparation method of nanoscale zirconium-doped lithium titanate material
CN105762346A (en) Preparation method of spherical lithium titanate-graphene composite material for cathodes of lithium ion batteries
CN102169980A (en) Preparation method of anode active material
CN106992295B (en) A kind of preparation method of monodisperse alpha-ferric oxide nanometer sheet
CN106784693A (en) A kind of surface has the preparation method of the rich nitrogen nano lithium titanate electrode material of uniform carbon coating layer
CN102229439B (en) Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material
CN105406071A (en) High-rate lithium vanadium phosphate positive electrode material, and preparation method and application thereof
CN106340400B (en) A kind of carbon coating rhombic system nano bar-shape Nb2O5Material and preparation method thereof
CN105006563B (en) Lithium ion battery anode active material Li2ZnTi3O8Preparation method
CN104934577B (en) Mesoporous Li3VO4/C nano ellipsoid composite material embedded into graphene network, and preparation method and application of composite material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant