CN107394141A - Li4Ti5O12Composite, preparation method and lithium ion battery - Google Patents

Li4Ti5O12Composite, preparation method and lithium ion battery Download PDF

Info

Publication number
CN107394141A
CN107394141A CN201710544770.6A CN201710544770A CN107394141A CN 107394141 A CN107394141 A CN 107394141A CN 201710544770 A CN201710544770 A CN 201710544770A CN 107394141 A CN107394141 A CN 107394141A
Authority
CN
China
Prior art keywords
composite
preparation
lithium
carbon material
ion battery
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.)
Pending
Application number
CN201710544770.6A
Other languages
Chinese (zh)
Inventor
张勇
路密
郑晓冬
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to CN201710544770.6A priority Critical patent/CN107394141A/en
Publication of CN107394141A publication Critical patent/CN107394141A/en
Pending legal-status Critical Current

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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of Li4Ti5O12Composite, preparation method and lithium ion battery, it is related to battery material technical field.A kind of Li4Ti5O12The preparation method of composite：Titanium source, lithium source and conductive carbon material are well mixed, obtain mixed powder, mixed powder obtains Li through high temperature process heat4Ti5O12Composite, one or more of the conductive carbon material in electrically conductive graphite, fullerene, CNT, graphene.Preparation method is simple, and production process is simple, easily operated.Obtained Li4Ti5O12Composite can effectively prevent particle agglomeration, improve the electric conductivity of material, significantly improve the chemical property of material.In addition the invention further relates to the Li4Ti5O12Lithium ion battery made from composite.

Description

Li4Ti5O12Composite, preparation method and lithium ion battery
Technical field
The present invention relates to battery material field, and more particularly to a kind of Li4Ti5O12Composite, preparation method and lithium from Sub- battery.
Background technology
With the fast development of global economy, the fossil fuel such as coal, oil and natural gas as main energy sources is increasingly withered Exhaust, environmental pollution constantly aggravates, and tap a new source of energy turns into the task of top priority with renewable and clean energy resource.And in numerous new energy skills In art, energy storage turns into the most key link.Although power lithium-ion battery is not a kind of system for producing the energy, because its The advantages such as cleaning, safety and facility play more and more important effect in national economy and daily life.
With commercialized embedding lithium carbon phase ratio, Li4Ti5O12The change of negative material removal lithium embedded process crystal volume is small, circulation is steady It is qualitative it is good, security is superior, there is higher security and stability and more preferable chemical property, and with the negative pole of alloy type Material is compared, Li4Ti5O12Price it is less expensive and prepare be easier.But Li4Ti5O12The electric conductivity of material is poor, limits Its high rate performance, its cycle performance is also unsatisfactory, hinders its large-scale use.
Inventor, which studies, to be found,, can effectively altogether more the methods of doping zwitterion and cladding by reducing particle size Mend Li4Ti5O12The performance deficiency of material, improve its chemical property.Most widely used at present is by carbon coating Li4Ti5O12Material Expect that CN104993118A discloses a kind of ion cathode material lithium Li to improve its chemical property4Ti5O12/ C synthesis side Method, add water to mix titanium dioxide and organic carbon source, mist projection granulating after ball-milling treatment, obtain carbon coating titanium dioxide powder；So Mist projection granulating after addition lithium source ball-milling treatment afterwards, obtains drying powder；High-temperature heat treatment is carried out again, is obtained by air current classifying Ion cathode material lithium Li4Ti5O12/C.But although carbon coating can improve the electrical conductivity of electrode material, carbon content excessively can The tap density of material is reduced, causes the reduction of energy density per unit volume, coated modified carbon Li4Ti5O12The high rate performance of material and follow Ring stability also still needs further to be potentiated and enhanced.
Inventor, which studies, to be found, Li4Ti5O12Electronic conductivity it is low, in general technique be utilized in material surface cladding Organic pyrolytic carbon of sucrose, glucose etc..But compared with the material of general poorly conductive, Li4Ti5O12Lithium-ion embeding it Afterwards, the electric conductivity of material can increase.The main function of the pyrolytic carbons such as sucrose is to prevent the Li in building-up process4Ti5O12Reunite and be Bigger particle, and the increase of grain diameter causes lithium ion to increase in solid interior diffusion length, so that the electrification of material Learn hydraulic performance decline.And conductive material is used as, the electric conductivity of the pyrolytic carbon of the organic matter of sucrose is not high.How further to improve Li4Ti5O12Electric conductivity, the chemical property for improving Li4Ti5O12 is significant.
The content of the invention
It is an object of the invention to provide a kind of Li4Ti5O12The preparation method of composite, in Li4Ti5O12Materials synthesis During add conductive material, effectively prevent cluster of grains coalescence improve material electric conductivity, preparation method is simple, easy to operate, Program is brief, is mass produced suitable for industrialization.
Another object of the present invention is to provide a kind of Li4Ti5O12Composite, this Li4Ti5O12Materials conductive performance is good, Electrochemical performance.
Third object of the present invention is to provide a kind of lithium ion battery, and this battery cost is cheap, superior performance.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of Li4Ti5O12The preparation method of composite, comprises the following steps：
Titanium source and lithium source are on the waiting list by certain stoichiometric proportion, titanium source, lithium source and conductive carbon material are well mixed and obtained Mixed powder, mixed powder obtain Li through high temperature process heat4Ti5O12Composite.Conductive carbon material be selected from electrically conductive graphite, One or more in fullerene, CNT, graphene.
The present invention proposes a kind of Li4Ti5O12Composite, it is prepared according to above-mentioned preparation method.
The present invention proposes a kind of lithium ion battery, including positive pole, negative pole and electrolyte, and negative pole includes above-mentioned Li4Ti5O12Composite.
The Li of the embodiment of the present invention4Ti5O12The beneficial effect of composite, preparation method and lithium ion battery is：
Li provided by the invention4Ti5O12Composite, the high for example conductive stone of carbon material of electric conductivity is added in building-up process Ink, CNT, graphene etc., or the mixture of the carbon material of the above-mentioned high conductivity of addition.Compared to pyrolytic carbons such as sucrose, The addition of the high conductive carbon material such as electrically conductive graphite, CNT can significantly improve the electric conductivity of material, improve material Chemical property so that the performance of material is greatly enhanced.The addition of conductive carbon material can effectively prevent particle Reunite, improve the electric conductivity between particle, further improve the performance of material.
In addition, in the preparation process of existing lithium ion battery, conductive carbon material is in electrode slurry preparation process The conductive agent that must be added.The present invention by by the species and content of conductive carbon material in Li4Ti5O12Building-up process in plus Enter, the Li containing conductive carbon material is prepared4Ti5O12Composite, therefore, in the preparation process of subsequent electrode slurry It can not add or add conductive agent less, reduce the ball milling or other mixed that active material is well mixed with conductive agent in subsequent handling Step is closed, and it is scattered to solve the problems, such as that conductive carbon material is difficult in electrode slurry preparation process, improves the matter of electrode slurry Amount, so as to obtain the lithium ion battery of function admirable.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the Li that the embodiment of the present invention 1 provides4Ti5O12The Li that composite and comparative example 1 provide4Ti5O12XRD Spectrum；
Fig. 2 is the Li that comparative example 1 of the present invention provides4Ti5O12SEM spectrum；
Fig. 3 is the Li that the embodiment of the present invention 1 provides4Ti5O12The SEM spectrum of composite；
Fig. 4 is the Li of test example of the present invention4Ti5O12The cycle performance test result figure of material；
Fig. 5 is the Li that the embodiment of the present invention 2 provides4Ti5O12The cycle performance figure of composite.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase Product.
Below to the Li of the embodiment of the present invention4Ti5O12Composite, preparation method and lithium ion battery are carried out specifically It is bright.
The present invention proposes a kind of Li4Ti5O12The preparation method of composite, comprises the following steps：
Titanium source, lithium source are on the waiting list by certain stoichiometric proportion, titanium source, lithium source and conductive carbon material are mixed Powder is closed, mixed powder obtains Li through high temperature process heat4Ti5O12Composite.Conductive carbon material is selected from electrically conductive graphite, richness Strangle the one or more in alkene, CNT, graphene.
The carbon materials such as electrically conductive graphite, fullerene, CNT, graphene are the carbon material of high conductivity.Pass through high temperature Solid-phase synthesis is in Li4Ti5O12Particle between fill a floor height conductive carbon material layer.The addition of high conductivity carbon material can Effectively to prevent particle agglomeration, the electric conductivity between particle is improved, further improves the performance of material.And compared to heat such as sucrose The addition of the solution high conductive carbon material such as carbon, electrically conductive graphite, CNT can significantly improve the electric conductivity of material, improve material The chemical property of material so that the performance of material is greatly enhanced.
Further, in present pre-ferred embodiments, titanium source is selected from nano titanium oxide.Nano titanium oxide disperses Performance is good, and reactivity is higher, and obtained material property is more excellent.It is understood that titanium dioxide can select sharp ore deposit Type titanium dioxide or rutile titanium dioxide.
Further, in present pre-ferred embodiments, lithium source is in lithium acetate, lithium carbonate, lithium nitrate, lithium hydroxide One or more.Preferably, using lithium carbonate or lithium acetate as lithium source.
Further, it is 0.7~0.9 by the mol ratio of lithium ion and titanium ion in present pre-ferred embodiments:1 adds Add lithium salts and titanium source.Under the mol ratio, Li can effectively ensure that4Ti5O12Synthesis, obtained material yield is more preferable, and quality is more It is good.Specifically, lithium salts and titanium source are stoichiometrically added.
Further, in present pre-ferred embodiments, the method for being well mixed is 8~12h of ball milling.The processing mode can So that all raw material is uniformly mixed, ensure product quality.High-energy ball milling method is effectively reduced the agglomeration of particle, Particle is polished using mechanical force, crushed simultaneously, grain diameter can be made to diminish, and is disperseed evenly.It is further preferable that 50 1~6h of ball milling under the conditions of~200r/min.Also wet-grinding technology and relative device can be used, the mass fraction 1 that added materials in mechanical milling process~ 1.5% nonionic surfactant, such as polyethylene glycol.Control ball milling speed and time, it is ensured that material is well mixed.It is non- The addition of ionic surface active agent can further promote the mix uniformly effect of raw material, and improve the reunion performance of material.
Further, in present pre-ferred embodiments, conductive carbon material is in Li4Ti5O12Quality point in composite Number is 0.5~10%.It is further preferable that the mass fraction of conductive carbon material is 3~5%.Under the ratio, Li4Ti5O12Table The carbon materials doses in face is suitable, and obtained material electrochemical performance reaches optimal.
Further, in present pre-ferred embodiments, it is 1 that conductive carbon material, which includes mass ratio,:1.5~3 carbon is received Mitron and electrically conductive graphite.In embodiments of the present invention, electrically conductive graphite selects Super P.Using two kinds of different high conductivity carbon Material, it can further improve electric conductivity, chemical property of material etc..And CNT has unique physical chemistry Can, such as unique metal or semiconducting electrical conductivity, high mechanical strength and hydrogen storage ability, adsorption capacity and the suction of wideband electromagnetic ripple Receive characteristic.The microstructure of CNT can make that Lithium-ion embeding depth is small, and process is short.
Further, in present pre-ferred embodiments, the material after ball milling is dried using spray drying process, more Condition to be preferably spray-dried is 180 DEG C, 3R/min, 60HZ.It can be consolidated by the particle of spray drying in subsequent high temperature Good spherical structure is kept in the step of being combined to, obtains sphericity height, uniform particle diameter, the good product of stability.
Further, in present pre-ferred embodiments, the condition of high temperature process heat is：Under inert gas atmosphere, 10~15h is calcined under the conditions of 700~900 DEG C.
Further, inert gas selects argon gas, nitrogen or other rare gas, and the heating rate in calcination process is 3~8 DEG C/min.It is further preferable that using temperature programmed control, 700~750 DEG C first are warming up to 5~8 DEG C/min speed, insulation 60~90min, 850~900 DEG C then are warming up to 1~2 DEG C/min, calcine 10~13h.Further, 350 after calcining Anneal 30~60min under the conditions of~450 DEG C.By the regulation and control to temperature and time during high temperature process heat, further carry The structural stability of high material, improve the chemical property of material.
The present invention proposes a kind of Li4Ti5O12Composite, it is prepared according to above-mentioned preparation method.
The present invention also proposes a kind of lithium ion battery, including positive pole, negative pole and electrolyte, and negative pole includes above-mentioned Li4Ti5O12Composite.
Further, in present pre-ferred embodiments, negative pole is prepared according to following methods：By Li4Ti5O12It is compound Material, bonding agent, solvent mixing, are made electrode slurry, and electrode slurry is compounded to form negative plate with collector.
Specifically, by Li4Ti5O12Composite, bonding agent (PVDF) are according to mass ratio 90:10 in 1-METHYLPYRROLIDONE (NMP) slurry is mixed and made into, is coated in by coating machine on the thick copper foil of affluxion body of 15um, it is small that 24 are dried in vacuo at 120 DEG C When, the thick pole pieces of 140um are then pressed on roll squeezer, finally cut into 101mm × 198mm negative plate.
The Li of the embodiment of the present invention4Ti5O12Composite is of the same race using that must be added in electrode slurry preparation process Class, the conductive agent (carbon material of high conductivity) with content, reduce rear process is that active material is mixed with conductive agent Uniform ball milling or other mixing steps, also solve conductive carbon material and are difficult to scattered ask in electrode slurry preparation process Topic, be advantageous to improve the quality of electrode slurry.
Further, in present pre-ferred embodiments, in electrode slurry, conductive carbon material composition and content exist Li4Ti5O12It is determined in advance in the preparation process of composite, controls Li4Ti5O12, conductive carbon material, the mass ratio of bonding agent For 85~95:2~10:3~5.Ratio of the conductive carbon material in electrode slurry is controlled, further improves lithium ion battery Performance, make it have good electric conductivity, high rate performance and cycle performance etc..
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of Li that the present embodiment provides4Ti5O12Composite, it is prepared according to following steps：
A certain amount of lithium carbonate, nano titanium oxide are stoichiometrically weighed respectively, and it is conductive to weigh a little Super P (final content is Li to carbon material4Ti5O12The 5wt% of composite), ball milling 2h obtains mixed powder, mixed powder in agate pot After body compacting under an argon atmosphere, 850 DEG C of calcining 12h finally obtain Li4Ti5O12Composite.
Embodiment 2
A kind of Li that the present embodiment provides4Ti5O12Composite, it is prepared according to following steps：
A certain amount of lithium carbonate, nano titanium oxide are stoichiometrically weighed respectively, and weigh mass ratio as 1:2 carbon (both final contents are Li for nanotube and Super P conductive carbon materials4Ti5O12The 3wt% of composite), in agate pot Ball milling 1.5h, ball milling speed 200r/min.Mixed powder, after mixed powder compacting under an argon atmosphere, 700 are obtained after ball milling DEG C calcining 13h finally obtain Li4Ti5O12Composite.
Embodiment 3
A kind of Li that the present embodiment provides4Ti5O12Composite, it is prepared according to following steps：
A certain amount of lithium acetate, nano titanium oxide are weighed respectively, wherein, the mol ratio of lithium ion and titanium ion is 0.8: 1.And mass ratio is weighed as 1:1:(the final content of three is for 3 graphene, CNT and Super P conductive carbon materials Li4Ti5O12The 10wt% of composite), the ball milling 3h in agate pot, ball milling speed 150r/min.Mixed after ball milling Powder, after mixed powder compacting under an argon atmosphere, 820 DEG C of calcining 14h finally obtain Li4Ti5O12Composite.
Embodiment 4
The present embodiment provides a kind of lithium ion battery, and it is prepared according to following steps：
By Li made from embodiment 14Ti5O12Composite and binding agent (PVDF) mix system in 1-METHYLPYRROLIDONE Into slurry.Control Li in slurry4Ti5O12, conductive carbon material, bonding agent mass ratio be 95:5:4.Slurry passes through coating machine It is coated on the thick copper foil of affluxion body of 15um, is dried in vacuo 24 hours at 120 DEG C, is then pressed into the thick pole pieces of 140um, cuts into 101mm × 198mm negative plate.
Using lithium piece as positive plate, positive and negative plate lamination is built up into battery core, each battery core is by 21 positive poles and 22 negative pole groups Into being dried in vacuo 24 hours at 80 DEG C, rush the techniques such as hole, welding, top side seal, fluid injection and sealing through aluminum plastic film, be made specified Capacity is 11Ah flexible packing lithium ion battery, and electrolyte is 1mol/L LiPF6/EC+DMC (1：1wt), barrier film Celgard 2320.LiMn is made after the processes such as chemical conversion (2-2.8V is circulated 3 times under 0.01C multiplying powers), vacuum seal, partial volume in battery2O4- Li4Ti5O12Flexible packing lithium ion battery finished product.
Embodiment 5
The present embodiment provides a kind of lithium ion battery, and it is prepared according to following steps：
With Li made from embodiment 14Ti5O12Composite is active material, by active material, conductive agent (Super P) Slurry is mixed and made into 1-METHYLPYRROLIDONE with binding agent (PVDF).Wherein, various solid contents in control control slurry The content of matter is Li4Ti5O12:Super P:PVdF=80:10:10.It is coated in by coating machine on the thick copper foil of affluxion body of 15um, It is dried in vacuo 24 hours at 120 DEG C, is then pressed into the thick pole pieces of 140um, cuts into 101mm × 198mm negative plate.
Using lithium piece as positive plate, positive and negative plate lamination is built up into battery core, each battery core is by 21 positive poles and 22 negative pole groups Into being dried in vacuo 24 hours at 80 DEG C, rush the techniques such as hole, welding, top side seal, fluid injection and sealing through aluminum plastic film, be made specified Capacity is 11Ah flexible packing lithium ion battery, and electrolyte is 1mol/L LiPF6/EC+DMC (1：1wt), barrier film Celgard 2320.LiMn is made after the processes such as chemical conversion (2-2.8V is circulated 3 times under 0.01C multiplying powers), vacuum seal, partial volume in battery2O4- Li4Ti5O12Flexible packing lithium ion battery finished product.
Comparative example 1
A kind of Li that this comparative example provides4Ti5O12Material, it is prepared according to following steps：
A certain amount of lithium carbonate, nano titanium oxide are stoichiometrically weighed respectively, the ball milling 2h in agate pot.Ball milling After obtain powder, 850 DEG C of calcining 12h finally obtain Li after powder-compacting under an argon atmosphere4Ti5O12Material.
Test example 1
XRD carries out thing phase test analysis to material made from embodiment 1 and comparative example 1.Fig. 1 is the XRD spectrum surveyed.
It can be obtained from Fig. 1, two samples have highly consistent diffraction maximum, in addition conductive carbon material well-crystallized, institute Some peaks are between 10-90 ° and can be with Li4Ti5O12Standard PDF cards match, and without other dephasign peaks, this Illustrate that no impurity or impurity content are very low.XRD spectrum illustrates that the addition of conductive carbon material does not change Li4Ti5O12Lattice Pattern.
Test example 2
The microscopic appearance of material made from embodiment 1 and comparative example 1 is observed using ESEM (SEM), tied Fruit is as shown in Figures 2 and 3.Fig. 2 (a) is Li made from comparative example 14Ti5O12Material, Fig. 2 (b) are putting at square frame in Fig. 2 (a) Big figure.Fig. 3 (a) is obtained Li4Ti5O12Composite, Fig. 3 (b) are the enlarged drawing at square frame in Fig. 3 (a).
It can be obtained by Fig. 2 and Fig. 3, Li made from comparative example 14Ti5O12Agglomeration is more serious, and made from embodiment 1 Li4Ti5O12Composite favorable dispersibility, it can obtain, the addition of conductive carbon material can effectively prevent Li4Ti5O12Reunion, Improve the chemical property of material.
Test example 3
Using material marking made from comparative example 1 as LTO-1, using material marking made from embodiment 1 as LTO-2, to implement Material made from example 1 sintered in 700 DEG C of air 3 hours using remove the material marking obtained after the conductive carbon material in material as LTO-3.Respectively using LTO-1, LTO-2, LTO-3 as active material, addition bonding agent PVdF and NMP are solvent, control slurry In the contents of various solid materials be Li4Ti5O12:Super P:PVdF=80:10:10, prepare electrode by collector of copper sheet And be assembled into button cell and be measured, the electrochemical property test result of three kinds of materials is as shown in Figure 4.
It can be obtained from Fig. 4, LTO-1 chemical property is poor, and LTO-2 chemical property is the most excellent.Although LTO-3 is in work Conductive carbon material is not contained in property material, but conductive carbon material is added with building-up process, effectively prevent Li4Ti5O12Reunion, so as to improve the chemical property of material.As can be seen here, conductive carbon material is added in building-up process Li can be effectively improved4Ti5O12Chemical property.
Test example 4
With Li made from embodiment 24Ti5O12Composite is active material, is assembled into 10Ah flexible packaging power battery, Preparation process of the preparation process with reference to embodiment 4.1000 cyclic curves of obtained lithium ion battery are as shown in Figure 5.The electricity The initial capacity in pond is 10.3Ah, and capacity is 10.15Ah after 1000 circulations, capability retention 98.5%.Thus It can be seen that Li made from the embodiment of the present invention4Ti5O12Composite excellent electrochemical performance.
In summary, the Li of the embodiment of the present invention4Ti5O12Carbon material of the composite due to adding high high conductivity, can To improve the electric conductivity between particle while particle agglomeration is prevented, the chemical property of material is significantly improved.In addition, system Preparation Method is simple, technique simplifies, and parameters are easily controlled, had broad application prospects.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made Every other embodiment, belongs to the scope of protection of the invention.

Claims (10)

  1. A kind of 1. Li4Ti5O12The preparation method of composite, it is characterised in that comprise the following steps：
    Titanium source and lithium source are on the waiting list by certain stoichiometric proportion, the titanium source, the lithium source and conductive carbon material are well mixed Mixed powder is obtained, the mixed powder obtains Li through high temperature process heat4Ti5O12Composite, the conductive carbon material One or more in electrically conductive graphite, fullerene, CNT, graphene.
  2. 2. Li according to claim 14Ti5O12The preparation method of composite, it is characterised in that the electric conductivity carbon materials Material is in the Li4Ti5O12Mass fraction is 0.5~10% in composite.
  3. 3. Li according to claim 14Ti5O12The preparation method of composite, it is characterised in that the electric conductivity carbon materials Material includes mass ratio for 1:1.5~3 CNT and electrically conductive graphite.
  4. 4. Li according to claim 14Ti5O12The preparation method of composite, it is characterised in that the titanium source is selected from and received Rice titanium dioxide.
  5. 5. Li according to claim 14Ti5O12The preparation method of composite, it is characterised in that the lithium source is selected from vinegar One or more in sour lithium, lithium carbonate, lithium nitrate, lithium hydroxide.
  6. 6. Li according to claim 14Ti5O12The preparation method of composite, it is characterised in that the high temperature solid-state is closed Into condition be：Under inert gas atmosphere, 10~15h is calcined under the conditions of 700~900 DEG C.
  7. A kind of 7. Li4Ti5O12Composite, it is characterised in that according to the preparation method system described in claim 1~6 any one It is standby to obtain.
  8. 8. a kind of lithium ion battery, it is characterised in that including positive pole, negative pole and electrolyte, the negative pole includes right such as will Seek the Li described in 14Ti5O12Composite.
  9. 9. lithium ion battery according to claim 8, it is characterised in that the negative pole is prepared according to following methods： By the Li4Ti5O12Composite, bonding agent, solvent mixing, are made electrode slurry, the electrode slurry and afflux bluk recombination Form negative plate.
  10. 10. lithium ion battery according to claim 9, it is characterised in that in the electrode slurry, conductive carbon material group Into with content in the Li4Ti5O12It is determined in advance in the preparation process of composite, controls Li4Ti5O12, conductive carbon material, The mass ratio of bonding agent is 85~95:2~10:3~5.
CN201710544770.6A 2017-07-06 2017-07-06 Li4Ti5O12Composite, preparation method and lithium ion battery Pending CN107394141A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710544770.6A CN107394141A (en) 2017-07-06 2017-07-06 Li4Ti5O12Composite, preparation method and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710544770.6A CN107394141A (en) 2017-07-06 2017-07-06 Li4Ti5O12Composite, preparation method and lithium ion battery

Publications (1)

Publication Number Publication Date
CN107394141A true CN107394141A (en) 2017-11-24

Family

ID=60335539

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710544770.6A Pending CN107394141A (en) 2017-07-06 2017-07-06 Li4Ti5O12Composite, preparation method and lithium ion battery

Country Status (1)

Country Link
CN (1) CN107394141A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108878853A (en) * 2018-07-11 2018-11-23 济南开发区星火科学技术研究院 A kind of preparation method of lithium titanate-graphene composite negative pole
CN110429324A (en) * 2019-08-05 2019-11-08 安徽相源新能源有限公司 A kind of preparation method of the modified compound lithium cell of high capacity
CN111082022A (en) * 2019-12-28 2020-04-28 石家庄昭文新能源科技有限公司 High-rate spherical oxide alloy composite electrode material and preparation method thereof
CN112166094A (en) * 2018-05-30 2021-01-01 魁北克电力公司 Ceramics, method for the production thereof and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102664252A (en) * 2012-05-19 2012-09-12 哈尔滨工业大学 Preparation method for cathode composite material Li4Ti5O12/AB/CNT of lithium ion battery
CN103682287A (en) * 2013-12-19 2014-03-26 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery silicon-based composite anode material, preparation method thereof and battery
CN105047863A (en) * 2015-06-09 2015-11-11 北京大学深圳研究生院 Cathode material for lithium battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102664252A (en) * 2012-05-19 2012-09-12 哈尔滨工业大学 Preparation method for cathode composite material Li4Ti5O12/AB/CNT of lithium ion battery
CN103682287A (en) * 2013-12-19 2014-03-26 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery silicon-based composite anode material, preparation method thereof and battery
CN105047863A (en) * 2015-06-09 2015-11-11 北京大学深圳研究生院 Cathode material for lithium battery and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112166094A (en) * 2018-05-30 2021-01-01 魁北克电力公司 Ceramics, method for the production thereof and use thereof
US11649190B2 (en) 2018-05-30 2023-05-16 Hydro-Quebec Ceramics, methods for the production thereof and uses of same
CN108878853A (en) * 2018-07-11 2018-11-23 济南开发区星火科学技术研究院 A kind of preparation method of lithium titanate-graphene composite negative pole
CN108878853B (en) * 2018-07-11 2021-06-25 济南开发区星火科学技术研究院 Preparation method of lithium titanate-graphene composite negative electrode material
CN110429324A (en) * 2019-08-05 2019-11-08 安徽相源新能源有限公司 A kind of preparation method of the modified compound lithium cell of high capacity
CN111082022A (en) * 2019-12-28 2020-04-28 石家庄昭文新能源科技有限公司 High-rate spherical oxide alloy composite electrode material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN104993125B (en) A kind of lithium ion battery negative material Fe3O4The preparation method of/Ni/C
CN102969492B (en) Carbon-coated doping modified lithium titanate and preparation method thereof
CN103872315B (en) A kind of preparation method of cobalt acid lithium composite positive pole of Ge-doped high-energy-density
CN107910529A (en) A kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding and preparation method thereof
CN105870438B (en) A kind of lithium secondary battery lithium-rich anode composite material and preparation method
CN103762354B (en) A kind of LiNi0.5Mn1.5O4 material, its preparation method and lithium ion battery
CN102496707A (en) Preparation method of nano-grade-carbon-clad spinel lithium titanate battery cathode material
CN104518207B (en) A kind of lithium ion battery anode active material and preparation method, anode and lithium ion battery
CN104037412B (en) The preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball
CN107394141A (en) Li4Ti5O12Composite, preparation method and lithium ion battery
CN103956475A (en) Method for preparing lithium titanate of lithium ion battery cathode material
CN104409715A (en) Preparation method of high-performance nitrogen-doped carbon-coated lithium titanate composite anode material of lithium ion battery
CN105870447A (en) Preparation method of nitrogen-doped rutile TiO2/C negative electrode material for sodium-ion battery
CN103337604A (en) Hollow spherical NiMn2O4 lithium ion battery cathode material and preparation method thereof
CN104993118A (en) Synthesizing method for lithium-ion negative electrode material of Li4Ti5O12/C
CN106207161A (en) Negative material and preparation method and with the lithium rechargeable battery of this negative material
CN104409712A (en) Preparation method of carbon and nitrogen coated lithium titanate material
CN102709548A (en) Multi-element cathode material for lithium ion battery and preparation method for multi-element cathode material
CN105098158A (en) Zirconium-doped lithium-rich cathode material of lithium ion battery and preparation method of zirconium-doped lithium-rich cathode material
CN103390748A (en) Preparation method for cladding lithium cobaltoxide cathode material with alumina
CN103746109B (en) A kind of method of liquid phase method coated lithium ion battery positive-material lithium manganate
CN107601579A (en) A kind of preparation method of high-performance porous C o Mn O nanometer sheet materials and its resulting materials and application
CN107069026A (en) A kind of rich lithium manganese oxide anode material of effective stratiform for suppressing capacity/voltage attenuation in cyclic process and its preparation method and application
CN104269520A (en) Li with graphene as carrier2FeTiO4-G composite cathode material and preparation method thereof
CN104183827B (en) A kind of lithium iron phosphate nano rod and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20171124