CN103762335A - Lithium titanate electrode plate and lithium ion battery - Google Patents

Lithium titanate electrode plate and lithium ion battery Download PDF

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Publication number
CN103762335A
CN103762335A CN201310750597.7A CN201310750597A CN103762335A CN 103762335 A CN103762335 A CN 103762335A CN 201310750597 A CN201310750597 A CN 201310750597A CN 103762335 A CN103762335 A CN 103762335A
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lithium titanate
coating
lithium
electrode slice
carbon
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CN103762335B (en
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李小兵
李文良
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Boke Energy System Shenzhen Co ltd
Shenzhen Highpower Technology Co Ltd
Springpower Technology Shenzhen Co Ltd
Huizhou Highpower Technology Co Ltd
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Boke Energy System Shenzhen Co ltd
Shenzhen Highpower Technology Co Ltd
Springpower Technology Shenzhen Co Ltd
Huizhou Highpower Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/62—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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a lithium titanate electrode plate and a lithium ion battery. The lithium titanate electrode plate comprises a current collector, a lithium titanate coating and a carbon coating, wherein the lithium titanate coating is stacked on the current collector, the carbon coating is stacked on the lithium titanate coating, and materials of the carbon coating include carbon materials, first binders and a first conductive agent. The electrolyte in the lithium ion battery reacts with the carbon coating under lower potential to form an SEI (solid electrolyte interface) film to separate active substances in the lithium titanate coating from the electrolyte, thus preventing battery ballooning caused by reaction between the active substances and the electrolyte due to overpotential; moreover, the carbon coating has certain lithium intercalation capacity, thus the transport of lithium ions is not affected; therefore, the lithium ion battery using the lithium titanate electrode plate has good cycle performance.

Description

Lithium titanate electrode slice and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of lithium titanate electrode slice and lithium ion battery.
Background technology
Lithium ion battery is a kind of rechargeable battery, and it mainly relies on lithium ion between positive pole and negative pole, to move work.Owing to having that operating voltage is high, specific energy is high, operating temperature range is wide and the advantage such as steady of discharging, lithium ion battery is widely used in the fields such as mobile communication equipment, panel computer, digital product, electric tool, automobile and energy-storage system.
Lithium titanate is a kind of material of spinel structure, because change in volume in the charge and discharge process that inserts, deviates from lithium ion is very little, almost nil, be called as " zero strain " material, and thering is discharge platform very stably, it approaches 1.55V to lithium current potential, is not easy to separate out Li dendrite, fail safe is very high, and the diffusion coefficient of lithium ion in lithium titanate crystal is 2 × 10 -8cm 2/ s, than the high order of magnitude of graphite cathode, can fast charging and discharging, lithium titanate material has become the study hotspot in lithium ion battery field at present.
But, lithium titanate embedding lithium current potential is high, be difficult to form SEI(solid electrolyte interface) film, in actual use, when especially carrying out compared with large current charge, be easy to produce overpotential, lithium titanate reacted with electrolyte and produce gas to cause battery bulging, affect the cycle performance of battery.
Summary of the invention
Based on this, be necessary to provide a kind of lithium titanate electrode slice, to solve the flatulence problem of lithium titanate battery, improve its cycle performance.
A kind of lithium titanate electrode slice, comprises collector, is laminated in the lithium titanate coating on described collector and is laminated in the carbon coating in described lithium titanate coating, the material of described carbon coating comprises material with carbon element, the first binding agent and the first conductive agent.
In an embodiment, described material with carbon element is selected from least one in Delanium, native graphite, soft carbon, carbonaceous mesophase spherules and hard carbon therein.
In an embodiment, the average grain diameter of described material with carbon element is 500 nanometer～5 micron therein.
In an embodiment, described the first binding agent is selected from least one in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber therein, and described the first conductive agent is acetylene black.
Therein in an embodiment, described carbon coating by mass percentage:
Described material with carbon element accounts for 80%～98%;
Described the first binding agent accounts for 0.5%～10%; And
Described the first conductive agent accounts for 0.5～10%.
In an embodiment, the thickness of described carbon coating is 10 microns～20 microns therein.
In an embodiment, the material of described lithium titanate coating comprises lithium titanate, the second binding agent and the second conductive agent therein.
In an embodiment, described the second binding agent is selected from least one in poly-inclined to one side fluorine vinyl chloride, carboxymethyl cellulose and butadiene-styrene rubber therein, and described the second conductive agent is acetylene black.
Therein in an embodiment, described lithium titanate coating by mass percentage:
Described lithium titanate accounts for 80%～98%;
Described the second binding agent accounts for 0.5%～10%; And
Described the second conductive agent accounts for 0.5～10%.
A kind of lithium ion battery, comprises housing, is arranged at battery core and filling electrolyte in described housing in described housing, and described battery core comprises the positive plate, barrier film and the negative plate that stack gradually, and described negative plate is above-mentioned lithium titanate electrode slice.
Above-mentioned lithium titanate electrode slice comprises and stacks gradually collector, lithium titanate coating and carbon coating, electrolyte is forming SEI film with carbon coating compared with reacting under electronegative potential, active material in lithium titanate coating and electrolyte are separated, prevent because overpotential causes active material and electrolyte react and cause battery bulging; And carbon coating has certain embedding lithium ability, does not affect the transportation of lithium ion.Therefore, this lithium titanate electrode slice can improve the cycle performance of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the structural representation of the lithium titanate electrode slice of an execution mode;
Fig. 2 is the cyclic curve comparison diagram of the lithium ion battery of embodiment 1 and the lithium ion battery of comparative example.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the lithium titanate electrode slice 100 of an execution mode, comprises carbon coating 10, lithium titanate coating 20 and collector 30.Lithium titanate coating 20 is laminated on collector 30, and carbon coating 10 is laminated in lithium titanate coating 20.
The material of carbon coating 10 comprises material with carbon element, the first binding agent and the first conductive agent.
Material with carbon element is the material with carbon element of small particle diameter.Preferably, the average grain diameter of material with carbon element (D50) is 500 nanometer～5 micron.
Preferably, material with carbon element is selected from least one in Delanium, native graphite, soft carbon, carbonaceous mesophase spherules and hard carbon.
The average grain diameter D50 of Delanium, native graphite, soft carbon, carbonaceous mesophase spherules and hard carbon is preferably 500 nanometer～5 micron.
The first binding agent is selected from least one in Kynoar (PVDF), carboxymethyl cellulose (CMC) and butadiene-styrene rubber (SBR).The first conductive agent is acetylene black.
This lithium titanate electrode slice 100 is applied to lithium ion battery as negative pole, after this lithium ion battery is carried out to precharge and changes into, because lithium titanate electrode slice 100 includes carbon coating 10, can form SEI film in negative terminal surface, prevent electrolyte and this lithium titanate electrode slice 100 Surface Contacts, avoid the active material in electrolyte and lithium titanate coating 20 to react, solved the problem of traditional lithium titanate battery aerogenesis; Meanwhile, SEI film itself is good lithium ion conductor, can not affect the performance of lithium ion battery.
In carbon coating 10, material with carbon element has the effect of embedding lithium, still can guarantee that lithium ion is in the interior normal transport of lithium titanate electrode slice 100 after making to arrange carbon coating 10, to realize lithium ion, normally inserts and deviates from, and does not affect the performance of lithium ion battery.
The first binding agent plays cementation, for bonded carbon material and the first conductive agent, and makes carbon coating 10 adhesion property in lithium titanate coating 20 better.
The first conductive agent is used for improving electric conductivity.The lithium titanate coating of tradition lithium ion battery all contains conductive agent, generally can not add extra conductive agent.Because carbon coating 10 covers the surface of lithium titanate coating 20, in order further to improve the migration rate of lithium ion, thereby improve charge-discharge velocity.In carbon coating 10, add the first appropriate conductive agent.
Preferably, in carbon coating 10, by mass percentage, material with carbon element accounts for 80%～98%, and the first binding agent accounts for 0.5%～10%, and the first conductive agent accounts for 0.5%～10%.
The material of lithium titanate coating 20 comprises lithium titanate, the second binding agent and the second conductive agent.
The second binding agent is selected from least one in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber, and the second conductive agent is acetylene black.
Preferably, in lithium titanate coating 20, by mass percentage, lithium titanate accounts for 80%～98%, and the second binding agent accounts for 0.5%～10%, and the second conductive agent accounts for 0.5～10%.
By said ratio, make lithium titanate coating 20 can realize preferably lithium ion and insert, deviate from, improve the performance of lithium ion battery.
Preferably, the thickness of lithium titanate coating 20 is 40 microns～200 microns.
Collector 30 is preferably Copper Foil or aluminium foil.
Lithium titanate electrode slice 100 is owing to being provided with the carbon coating 10 being laminated in lithium titanate coating 20, electrolyte is forming SEI film with carbon coating 10 compared with reacting under electronegative potential, active material in lithium titanate coating 20 and electrolyte are separated, prevent because overpotential causes active material and electrolyte react and cause battery bulging, SEI film itself is good lithium ion conductor, can not affect the performance of lithium ion battery.
And carbon coating 10, owing to comprising material with carbon element, has certain embedding lithium ability, does not affect the transportation of lithium ion.Therefore, this lithium titanate electrode slice 100 can improve the cycle performance of lithium ion battery.
The thickness of carbon coating 10 is too little, and preparation technology requires high; The thickness of carbon coating 10 is too large, is unfavorable for bringing into play the advantage of lithium titanate coating 20.Therefore, preferably, the thickness of carbon coating 10 is 10 microns～20 microns.
More preferably, the thickness of carbon coating 10 is 15 microns.
Above-mentioned lithium titanate electrode slice 100 is compared with lithium titanate anode surface-coated insulation oxide, by form carbon coating 10 in lithium titanate coating 20, after lithium ion battery is carried out to precharge and changes into, in negative terminal surface, form SEI film, prevent that electrolyte from contacting and reacting with electrode surface, solved the problem of lithium titanate battery aerogenesis; Meanwhile, SEI film itself is good lithium ion conductor, can not affect the performance of battery.
Above-mentioned lithium titanate electrode slice 100, compared with carrying out the coated lithium titanate material of carbon in microcosmic point, is in lithium titanate coating 20, to form carbon coating 10, can avoid the problem of the coated inhomogeneous performance that affects battery.
Above-mentioned lithium titanate electrode slice 100 is prepared as follows:
Step S110: prepare lithium titanate coating paste.
Lithium titanate, the second binding agent and the second conductive agent are added in the second solvent, stir and obtain lithium titanate coating paste.
Preferably, the mass ratio of lithium titanate, the second binding agent and the second conductive agent is 80～98:0.5～10:0.5～10.
The second solvent is 1-METHYLPYRROLIDONE or water.
Step S120: lithium titanate coating paste is coated on collector, forms lithium titanate coating after being dried on collector.
Preferably, dry under 80 ℃～110 ℃ conditions, make the second solvent evaporates, on collector, form lithium titanate coating.
Mixing speed is preferably 3000r/min～5000r/min.
Step S130: prepare carbon coating slurry.
Material with carbon element, the first binding agent and the first conductive agent are added in the first solvent, stir and obtain carbon coating slurry.
Preferably, the mass ratio of material with carbon element, the first binding agent and the first conductive agent is 80～98:0.5～10:0.5～10.
The first solvent is 1-METHYLPYRROLIDONE or water.
Mixing speed is preferably 3000r/min～5000r/min.
Step S140: carbon coating slurry is coated in lithium titanate coating, forms carbon coating after being dried in lithium titanate coating, obtain lithium titanate electrode slice.
Preferably, dry under 80 ℃～110 ℃ conditions, make the first solvent evaporates, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice.
The lithium ion battery of one execution mode, comprises housing, is arranged at battery core and filling electrolyte in housing in housing.
Battery core comprises the positive plate, barrier film and the negative plate that stack gradually.
Positive plate comprises collector and is laminated in the anodal active layer on collector.The material of anodal active layer comprises positive electrode active materials, conductive agent and binding agent.Positive electrode active materials is selected from least one in cobalt acid lithium, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate and nickel LiMn2O4.
Negative plate is above-mentioned lithium titanate electrode slice 100.
Carbon coating 10 in negative plate reacts formation SEI film with electrolyte need to consume lithium ion, therefore anodal excessive design.Preferably, anodal excessive design ratio is 1.01～1.25.
Prepare as follows above-mentioned lithium ion battery:
Positive plate, barrier film and negative plate are stacked gradually and reel after pack in shell, in shell, inject electrolyte, be assembled into lithium ion battery.After having assembled, change into, the system that changes into is that cut-off current is 0.01C～0.05C in 0.1C～5C constant-current constant-voltage charging to 2.8V～4.0V.
Above-mentioned lithium ion battery, owing to using above-mentioned lithium titanate electrode slice 100 as negative plate, has solved the problem of traditional lithium titanate battery aerogenesis.Therefore, the cycle performance of this lithium ion battery is better.
By specific embodiment, further set forth below.
Embodiment 1
Prepare lithium titanate electrode slice and lithium ion battery
1, get 100g Kynoar binding agent, 20g acetylene black conductor and 2kg lithium titanate, be dispersed in 2kg 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 3000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on Copper Foil, under 90 ℃ of conditions, dries, form lithium titanate coating on Copper Foil, the thickness of lithium titanate coating is 150 microns;
3, getting 10g Kynoar binding agent, 15g acetylene black conductor and average grain diameter is 500 nanometer 200g Delaniums, is dispersed in 200g 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 3000r/min, disperses, and stirs and obtains carbon coating slurry;
4, carbon coating slurry is coated in lithium titanate coating, under 90 ℃ of conditions, dries, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice; Wherein, the thickness of carbon coating is 15 microns;
5, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is LiMn2O4, Kynoar binding agent and the acetylene black conductor of 1:50:10, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.1C electric current constant current constant voltage to change into 3.9V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 98%.
Embodiment 2
Prepare lithium titanate electrode slice and lithium ion battery
1, get 60g Kynoar binding agent, 30g acetylene black conductor and 2kg lithium titanate, be dispersed in 2.5kg 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 4000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on Copper Foil, under 95 ℃ of conditions, dries, form lithium titanate coating on Copper Foil, the thickness of lithium titanate coating is 80 microns;
3, get the 200g Delanium that 15g Kynoar binding agent, 15g acetylene black conductor and average grain diameter are 800 nanometers, be dispersed in 220g 1-METHYLPYRROLIDONE, rotating speed high-speed stirred with 3500r/min is disperseed, and stirs and obtains carbon coating slurry;
4, carbon coating slurry is coated in lithium titanate coating, under 100 ℃ of conditions, dries, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice; Wherein, the thickness of carbon coating is 14 microns;
5, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is nickle cobalt lithium manganate, Kynoar binding agent and the acetylene black conductor of 1:30:15, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.2C electric current constant current constant voltage to change into 3.8V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 99%.
Embodiment 3
Prepare lithium titanate electrode slice and lithium ion battery
1, get 10g Kynoar binding agent, 10g acetylene black conductor and 0.98kg lithium titanate, be dispersed in 2.3kg 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 3000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on Copper Foil, under 105 ℃ of conditions, dries, form lithium titanate coating on Copper Foil, the thickness of lithium titanate coating is 60 microns;
3, getting 5g Kynoar binding agent, 9g acetylene black conductor and average grain diameter is the soft carbon of 190g of 1 micron, is dispersed in 250g 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 5000r/min, disperses, and stirs and obtains carbon coating slurry;
4, carbon coating slurry is coated in lithium titanate coating, under 110 ℃ of conditions, dries, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice; Wherein, the thickness of carbon coating is 13 microns;
5, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is nickle cobalt lithium manganate, Kynoar binding agent and the acetylene black conductor of 1:40:20, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.3C electric current constant current constant voltage to change into 3.7V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 98%.
Embodiment 4
Prepare lithium titanate electrode slice and lithium ion battery
1, get 100g Kynoar binding agent, 20g acetylene black conductor and 0.88kg lithium titanate, be dispersed in 200g 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 3000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on aluminium foil, under 85 ℃ of conditions, dries, form lithium titanate coating on aluminium foil, the thickness of lithium titanate coating is 100 microns;
3, getting 18g Kynoar binding agent, 2g acetylene black conductor and average grain diameter is the 380g hard carbon of 2 microns, is dispersed in 400g 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 5000r/min, disperses, and stirs and obtains carbon coating slurry;
4, carbon coating slurry is coated in lithium titanate coating, under 90 ℃ of conditions, dries, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice; Wherein, the thickness of carbon coating is 16 microns;
5, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is LiMn2O4, Kynoar binding agent and the acetylene black conductor of 1:50:10, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.4C electric current constant current constant voltage to change into 3.6V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 97%.
Embodiment 5
Prepare lithium titanate electrode slice and lithium ion battery
1, get 50g Kynoar binding agent, 10g acetylene black conductor and 0.94kg lithium titanate, be dispersed in 2.1kg 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 4000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on aluminium foil, under 95 ℃ of conditions, dries, form lithium titanate coating on aluminium foil, the thickness of lithium titanate coating is 120 microns;
3, getting 30g Kynoar binding agent, 15g acetylene black conductor and average grain diameter is the 600g carbonaceous mesophase spherules of 5 microns, be dispersed in 600g 1-METHYLPYRROLIDONE, rotating speed high-speed stirred with 4000r/min is disperseed, and stirs and obtains carbon coating slurry;
4, carbon coating slurry is coated in lithium titanate coating, under 90 ℃ of conditions, dries, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice; Wherein, the thickness of carbon coating is 15 microns;
5, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is nickel cobalt lithium aluminate, Kynoar binding agent and the acetylene black conductor of 1:50:10, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.4C electric current constant current constant voltage to change into 3.6V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 98%.
Embodiment 6
Prepare lithium titanate electrode slice and lithium ion battery
1, get 100g Kynoar binding agent, 100g acetylene black conductor and 0.8kg lithium titanate, be dispersed in 2.1kg 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 4000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on Copper Foil, under 95 ℃ of conditions, dries, form lithium titanate coating on Copper Foil, the thickness of lithium titanate coating is 120 microns;
3, getting 20g Kynoar binding agent, 10g acetylene black conductor, 400g average grain diameter is that the Delanium of 3 microns and 400g average grain diameter are the native graphite of 3 microns, be dispersed in 800g 1-METHYLPYRROLIDONE, rotating speed high-speed stirred with 4000r/min is disperseed, and stirs and obtains carbon coating slurry;
4, carbon coating slurry is coated in lithium titanate coating, under 90 ℃ of conditions, dries, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice; Wherein, the thickness of carbon coating is 10 microns;
5, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is nickle cobalt lithium manganate, Kynoar binding agent and the acetylene black conductor of 1:50:10, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.5C electric current constant current constant voltage to change into 3.6V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 99%.
Embodiment 7
Prepare lithium titanate electrode slice and lithium ion battery
1, get 40g carboxymethyl cellulose binding agent, 60g butadiene-styrene rubber binding agent, 5g acetylene black conductor and 0.895kg lithium titanate, be dispersed in 2kg water, with the rotating speed high-speed stirred of 4000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on Copper Foil, under 80 ℃ of conditions, dries, form lithium titanate coating on Copper Foil, the thickness of lithium titanate coating is 200 microns;
3, getting 2g carboxymethyl cellulose binding agent, 2g butadiene-styrene rubber binding agent, 1g acetylene black conductor and 98g average grain diameter is the hard carbon of 4 microns, is dispersed in 200g water, with the rotating speed high-speed stirred of 4000r/min, disperses, and stirs and obtains carbon coating slurry;
4, carbon coating slurry is coated in lithium titanate coating, under 80 ℃ of conditions, dries, in lithium titanate coating, form carbon coating, obtain lithium titanate electrode slice; Wherein, the thickness of carbon coating is 20 microns;
5, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is cobalt acid lithium, Kynoar binding agent and the acetylene black conductor of 1:50:10, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.1C electric current constant current constant voltage to change into 3.9V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 98%.
Comparative example
Prepare lithium titanate electrode slice and lithium ion battery
1, get 100g Kynoar binding agent, 20g acetylene black conductor and 2kg lithium titanate, be dispersed in 2kg 1-METHYLPYRROLIDONE, with the rotating speed high-speed stirred of 3000r/min, disperse, stir and obtain lithium titanate coating paste;
2, lithium titanate coating paste is coated on Copper Foil, under 90 ℃ of conditions, dries, on Copper Foil, form lithium titanate coating, obtain lithium titanate electrode slice; Wherein, the thickness of lithium titanate coating is 150 microns;
3, provide positive plate and negative plate, positive plate comprises aluminium foil and is laminated in anodal active layer on aluminium foil.The material of anodal active layer comprises that mass ratio is LiMn2O4, Kynoar binding agent and the acetylene black conductor of 1:50:10, and negative plate is above-mentioned lithium titanate electrode slice.After coiling, fluid injection, be assembled into lithium ion battery, use 0.1C electric current constant current constant voltage to change into 3.9V, cut-off current 0.05C.500 weeks rear capability retentions of 1C circulation are 82%.
The cyclic curve of the lithium ion battery of embodiment 1 and the lithium ion battery of comparative example contrasts referring to Fig. 2.As seen from Figure 2, the cycle performance of the lithium ion battery of embodiment 1 is better than the cycle performance of the lithium ion battery of comparative example.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a lithium titanate electrode slice, is characterized in that, comprises collector, is laminated in the lithium titanate coating on described collector and is laminated in the carbon coating in described lithium titanate coating, and the material of described carbon coating comprises material with carbon element, the first binding agent and the first conductive agent.
2. lithium titanate electrode slice according to claim 1, is characterized in that, described material with carbon element is selected from least one in Delanium, native graphite, soft carbon, carbonaceous mesophase spherules and hard carbon.
3. lithium titanate electrode slice according to claim 1 and 2, is characterized in that, the average grain diameter of described material with carbon element is 500 nanometer～5 micron.
4. lithium titanate electrode slice according to claim 1, is characterized in that, described the first binding agent is selected from least one in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber, and described the first conductive agent is acetylene black.
5. lithium titanate electrode slice according to claim 1, is characterized in that, described carbon coating by mass percentage:
Described material with carbon element accounts for 80%～98%;
Described the first binding agent accounts for 0.5%～10%; And
Described the first conductive agent accounts for 0.5～10%.
6. lithium titanate electrode slice according to claim 1, is characterized in that, the thickness of described carbon coating is 10 microns～20 microns.
7. lithium titanate electrode slice according to claim 1, is characterized in that, the material of described lithium titanate coating comprises lithium titanate, the second binding agent and the second conductive agent.
8. lithium titanate electrode slice according to claim 7, is characterized in that, described the second binding agent is selected from least one in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber, and described the second conductive agent is acetylene black.
9. lithium titanate electrode slice according to claim 7, is characterized in that, described lithium titanate coating by mass percentage:
Described lithium titanate accounts for 80%～98%;
Described the second binding agent accounts for 0.5%～10%; And
Described the second conductive agent accounts for 0.5～10%.
10. a lithium ion battery, comprise housing, be arranged at battery core and filling electrolyte in described housing in described housing, described battery core comprises the positive plate, barrier film and the negative plate that stack gradually, it is characterized in that, described negative plate is the lithium titanate electrode slice as described in claim 1～9 any one.
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