CN103762335B - 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
CN103762335B
CN103762335B CN201310750597.7A CN201310750597A CN103762335B CN 103762335 B CN103762335 B CN 103762335B CN 201310750597 A CN201310750597 A CN 201310750597A CN 103762335 B CN103762335 B CN 103762335B
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lithium titanate
coating
lithium
electrode plate
carbon
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CN103762335A (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

Abstract

The present invention relates to a kind of lithium titanate electrode plate and lithium ion battery.Lithium titanate electrode plate includes collector, be laminated on described collector lithium titanate coating and be laminated in the carbon coating in described lithium titanate coating, the material of described carbon coating includes material with carbon element, the first binding agent and the first conductive agent.Electrolyte in lithium ion battery and carbon coating react formation SEI film under relatively electronegative potential, are separated with electrolyte by the active substance in lithium titanate coating, prevent because overpotential causes active substance and electrolyte to react and cause battery tympanites；Further, carbon coating has certain embedding lithium ability, does not affect the transport of lithium ion.Therefore, the lithium ion battery using this lithium titanate electrode plate has good cycle performance.

Description

Lithium titanate electrode plate 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 plate and lithium ion Battery.
Background technology
Lithium ion battery is a kind of rechargeable battery, and it is mobile next between a positive electrode and a negative electrode that it relies primarily on lithium ion Work.Owing to having that running voltage is high, specific energy high, operating temperature range width and the electric discharge advantage such as steadily, Lithium ion battery be widely used in mobile communication equipment, panel computer, digital product, electric tool, automobile with And the field such as energy-storage system.
Lithium titanate is the material of a kind of spinel structure, due to the charge and discharge process inserted at lithium ion, deviate from Middle change in volume is the least, almost nil, is referred to as " zero strain " material, and it is flat to have electric discharge very smoothly Platform, its to lithium current potential close to 1.55V, it is not easy to separating out Li dendrite, safety is the highest, and lithium ion is at metatitanic acid Diffusion coefficient in crystalline lithium is 2 × 10-8cm2/ s, higher an order of magnitude than graphite cathode, can quickly charge and discharge Electricity, current lithium titanate material has become as the study hotspot of field of lithium ion battery.
But, lithium titanate intercalation potential is high, is hardly formed SEI(solid electrolyte interface) film, During actually used, the when of especially carrying out larger current charging, it is easy to produce overpotential so that Lithium titanate reacts with electrolyte and produces gas and causes battery tympanites, affects the cycle performance of battery.
Summary of the invention
Based on this, it is necessary to provide a kind of lithium titanate electrode plate, to solve the flatulence problem of lithium titanate battery, Improve its cycle performance.
A kind of lithium titanate electrode plate, the lithium titanate coating including collector, being laminated on described collector and layer Being laminated on the carbon coating in described lithium titanate coating, the material of described carbon coating includes material with carbon element, the first binding agent With the first conductive agent.
Wherein in an embodiment, described material with carbon element is selected from Delanium, native graphite, soft carbon, centre At least one in phase carbosphere and hard carbon.
Wherein in an embodiment, the mean diameter of described material with carbon element is 500 nanometers～5 microns.
Wherein in an embodiment, described first binding agent selected from Kynoar, carboxymethyl cellulose and At least one in butadiene-styrene rubber, described first conductive agent is acetylene black.
Wherein in an embodiment, described carbon coating by mass percentage:
Described material with carbon element accounts for 80%～98%；
Described first binding agent accounts for 0.5%～10%；And
Described first conductive agent accounts for 0.5～10%.
Wherein in an embodiment, the thickness of described carbon coating is 10 microns～20 microns.
Wherein in an embodiment, the material of described lithium titanate coating include lithium titanate, the second binding agent and Second conductive agent.
Wherein in an embodiment, described second binding agent is selected from poly-inclined fluorine vinyl chloride, carboxymethyl cellulose And at least one in butadiene-styrene rubber, described second conductive agent is acetylene black.
Wherein in an embodiment, described lithium titanate coating by mass percentage:
Described lithium titanate accounts for 80%～98%；
Described second binding agent accounts for 0.5%～10%；And
Described second conductive agent accounts for 0.5～10%.
A kind of lithium ion battery, the battery core including housing, being arranged in described housing and fill are in described housing Interior electrolyte, described battery core includes positive plate, barrier film and the negative plate stacked gradually, and described negative plate is Above-mentioned lithium titanate electrode plate.
Above-mentioned lithium titanate electrode plate includes stacking gradually collector, lithium titanate coating and carbon coating, electrolyte with Carbon coating reacts formation SEI film under relatively electronegative potential, by the active substance in lithium titanate coating and electrolyte every Open, prevent because overpotential causes active substance and electrolyte to react and cause battery tympanites；Further, Carbon coating has certain embedding lithium ability, does not affect the transport of lithium ion.Therefore, this lithium titanate electrode plate can Improve the cycle performance of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the structural representation of the lithium titanate electrode plate of an embodiment；
Fig. 2 is the lithium ion battery cyclic curve comparison diagram with the lithium ion battery of comparative example of embodiment 1.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, the most right The detailed description of the invention of the present invention is described in detail.Elaborate in the following description a lot of detail with It is easy to fully understand the present invention.But the present invention can come real to be a lot different from alternate manner described here Executing, those skilled in the art can do similar improvement in the case of intension of the present invention, therefore this Bright do not limited by following public being embodied as.
Referring to Fig. 1, the lithium titanate electrode plate 100 of an embodiment, including 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 In coating 20.
The material of carbon coating 10 includes 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.Preferably, the mean diameter (D50) of material with carbon element is 500 nanometers ～5 microns.
Preferably, material with carbon element is in Delanium, native graphite, soft carbon, carbonaceous mesophase spherules and hard carbon At least one.
Mean diameter D50 of Delanium, native graphite, soft carbon, carbonaceous mesophase spherules and hard carbon is preferably 500 nanometers～5 microns.
First binding agent is selected from Kynoar (PVDF), carboxymethyl cellulose (CMC) and butadiene-styrene rubber (SBR) at least one in.First conductive agent is acetylene black.
This lithium titanate electrode plate 100 is applied to lithium ion battery as negative pole, this lithium ion battery is carried out After precharge chemical conversion, owing to lithium titanate electrode plate 100 includes carbon coating 10, it is possible to formed in negative terminal surface SEI film, prevents electrolyte from contacting with this lithium titanate electrode plate 100 surface, it is to avoid electrolyte and lithium titanate coating Active substance in 20 reacts, the problem solving traditional lithium titanate battery aerogenesis；Meanwhile, SEI Film itself is good lithium ion conductor, does not interferes with the performance of lithium ion battery.
In carbon coating 10, material with carbon element has embedding lithium effect so that still ensure that after carbon coating 10 is set lithium from Son normal transport in lithium titanate electrode plate 100, normally inserts and deviates from realizing lithium ion, not affecting lithium The performance of ion battery.
First binding agent plays cementation, is used for bond material with carbon element and the first conductive agent, and makes carbon coating 10 exist In lithium titanate coating 20, adhesion property is preferable.
First conductive agent is used for improving electric conductivity.The lithium titanate coating of conventional lithium ion battery all contains conduction Agent, typically will not add extra conductive agent.Owing to carbon coating 10 covers the surface of lithium titanate coating 20, In order to improve the migration rate of lithium ion further, thus 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%, the first bonding Agent accounts for 0.5%～10%, and the first conductive agent accounts for 0.5%～10%.
The material of lithium titanate coating 20 includes lithium titanate, the second binding agent and the second conductive agent.
At least one in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber of second binding agent, the Two conductive agents are acetylene black.
Preferably, in lithium titanate coating 20, by mass percentage, lithium titanate accounts for 80%～98%, 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 preferably realize lithium ion and insert, deviate from, improve lithium The performance of 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 plate 100 is owing to being provided with the carbon coating 10 being laminated in lithium titanate coating 20, electrolyte With carbon coating 10 react under relatively electronegative potential formation SEI film, by the active substance in lithium titanate coating 20 with Electrolyte separates, and prevents because overpotential causes active substance and electrolyte to react and cause battery tympanites, SEI film itself is good lithium ion conductor, does not interferes with the performance of lithium ion battery.
Further, carbon coating 10, owing to comprising material with carbon element, has certain embedding lithium ability, does not affect the fortune of lithium ion Defeated.Therefore, this lithium titanate electrode plate 100 can improve the cycle performance of lithium ion battery.
The thickness of carbon coating 10 is the least, and preparation technology requires height；The thickness of carbon coating 10 is too big, is unfavorable for Play the advantage of lithium titanate coating 20.It is therefore preferred that the thickness of carbon coating 10 is 10 microns～20 micro- Rice.
It is highly preferred that the thickness of carbon coating 10 is 15 microns.
Above-mentioned lithium titanate electrode plate 100 is compared with lithium titanate anode surface-coated insulation oxide, by titanium Carbon coating 10 is formed, after lithium ion battery is carried out precharge chemical conversion, in negative terminal surface shape on acid lithium coating 20 Become SEI film, prevent electrolyte from contacting with electrode surface and react, solve asking of lithium titanate battery aerogenesis Topic；Meanwhile, SEI film itself is good lithium ion conductor, does not interferes with the performance of battery.
Above-mentioned lithium titanate electrode plate 100 compared with the lithium titanate material carrying out carbon cladding in microcosmic point, be Carbon coating 10, the problem that can avoid being coated with the uneven performance affecting battery is formed in lithium titanate coating 20.
Above-mentioned lithium titanate electrode plate 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, is uniformly mixing to obtain metatitanic acid Lithium coating slurry.
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.
Second solvent is N-Methyl pyrrolidone or water.
Step S120: be coated on collector by lithium titanate coating paste, forms titanium the most on a current collector Acid lithium coating.
Preferably, it is dried under the conditions of 80 DEG C～110 DEG C, makes the second solvent volatilization, form titanium on a current collector Acid lithium 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, is uniformly mixing to obtain carbon and is coated with Layer 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.
First solvent is N-Methyl pyrrolidone or water.
Mixing speed is preferably 3000r/min～5000r/min.
Step S140: carbon coating slurry is coated in lithium titanate coating, after drying shape in lithium titanate coating Become carbon coating, obtain lithium titanate electrode plate.
Preferably, it is dried under the conditions of 80 DEG C～110 DEG C, makes the first solvent volatilization, shape in lithium titanate coating Become carbon coating, obtain lithium titanate electrode plate.
The lithium ion battery of one embodiment, the battery core including housing, being arranged in housing and fill are in housing Interior electrolyte.
Battery core includes positive plate, barrier film and the negative plate stacked gradually.
Positive plate includes collector and the positive-active layer being laminated on collector.The material bag of positive-active layer Include positive electrode active materials, conductive agent and binding agent.Positive electrode active materials is selected from cobalt acid lithium, LiMn2O4, phosphoric acid At least one in ferrum lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate and nickel ion doped.
Negative plate is above-mentioned lithium titanate electrode plate 100.
Carbon coating 10 in negative plate and electrolyte react formation SEI film and need to consume lithium ion, therefore positive pole Excessive design.Preferably, positive pole excessive design coefficient is 1.01～1.25.
Prepare above-mentioned lithium ion battery as follows:
Load after positive plate, barrier film and negative plate are stacked gradually and wind in shell, in shell, inject electricity Solve liquid, be assembled into lithium ion battery.Being melted into after being completed, fertilizer alleviant is in 0.1C～5C constant current Constant-voltage charge is to 2.8V～4.0V, and cut-off current is 0.01C～0.05C.
Above-mentioned lithium ion battery, owing to use above-mentioned lithium titanate electrode plate 100 is as negative plate, solves tradition The problem of lithium titanate battery aerogenesis.Therefore, the cycle performance of this lithium ion battery is preferable.
It is expanded on further below by way of specific embodiment.
Embodiment 1
Preparation lithium titanate electrode plate and lithium ion battery
1,100g Kynoar binding agent, 20g acetylene black conductor and 2kg lithium titanate are taken, dispersed In 2kg N-Methyl pyrrolidone, disperse with the rotating speed high-speed stirred of 3000r/min, be uniformly mixing to obtain titanium Acid lithium coating slurry；
2, lithium titanate coating paste is coated on Copper Foil, dries under the conditions of 90 DEG C, Copper Foil is formed titanium Acid lithium coating, the thickness of lithium titanate coating is 150 microns；
3, taking 10g Kynoar binding agent, 15g acetylene black conductor is 500 nanometers 200g with mean diameter Delanium, is dispersed in 200g N-Methyl pyrrolidone, with the rotating speed high-speed stirred of 3000r/min Dispersion, is uniformly mixing to obtain carbon coating slurry；
4, carbon coating slurry is coated in lithium titanate coating, dries under the conditions of 90 DEG C, in lithium titanate coating Upper formation carbon coating, obtains lithium titanate electrode plate；Wherein, the thickness of carbon coating is 15 microns；
5, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes that mass ratio is the LiMn2O4 of 1:50:10, Kynoar binding agent and acetylene unlicensed tour guide Electricity agent, negative plate is above-mentioned lithium titanate electrode plate.After winding, fluid injection, it is assembled into lithium ion battery, makes With 0.1C electric current constant current constant voltage chemical conversion to 3.9V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity keeps Rate is 98%.
Embodiment 2
Preparation lithium titanate electrode plate and lithium ion battery
1,60g Kynoar binding agent, 30g acetylene black conductor and 2kg lithium titanate are taken, dispersed In 2.5kg N-Methyl pyrrolidone, disperse with the rotating speed high-speed stirred of 4000r/min, be uniformly mixing to obtain Lithium titanate coating paste；
2, lithium titanate coating paste is coated on Copper Foil, dries under the conditions of 95 DEG C, Copper Foil is formed titanium Acid lithium coating, the thickness of lithium titanate coating is 80 microns；
3, taking 15g Kynoar binding agent, 15g acetylene black conductor is 800 nanometers with mean diameter 200g Delanium, is dispersed in 220g N-Methyl pyrrolidone, with the rotating speed high speed of 3500r/min Dispersed with stirring, is uniformly mixing to obtain carbon coating slurry；
4, carbon coating slurry is coated in lithium titanate coating, dries under the conditions of 100 DEG C, be coated with at lithium titanate Form carbon coating on Ceng, obtain lithium titanate electrode plate；Wherein, the thickness of carbon coating is 14 microns；
5, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes that mass ratio is the nickle cobalt lithium manganate of 1:30:15, Kynoar binding agent and acetylene Black conductive agent, negative plate is above-mentioned lithium titanate electrode plate.It is assembled into lithium ion battery after winding, fluid injection, 0.2C electric current constant current constant voltage is used to be melted into 3.8V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity is protected Holdup is 99%.
Embodiment 3
Preparation lithium titanate electrode plate and lithium ion battery
1, take 10g Kynoar binding agent, 10g acetylene black conductor and 0.98kg lithium titanate, uniformly divide It is dispersed in 2.3kg N-Methyl pyrrolidone, disperses with the rotating speed high-speed stirred of 3000r/min, stir To lithium titanate coating paste；
2, lithium titanate coating paste is coated on Copper Foil, dries under the conditions of 105 DEG C, Copper Foil is formed Lithium titanate coating, the thickness of lithium titanate coating is 60 microns；
3, the 190g that 5g Kynoar binding agent, 9g acetylene black conductor and mean diameter are 1 micron is taken Soft carbon, is dispersed in 250g N-Methyl pyrrolidone, disperses with the rotating speed high-speed stirred of 5000r/min, It is uniformly mixing to obtain carbon coating slurry；
4, carbon coating slurry is coated in lithium titanate coating, dries under the conditions of 110 DEG C, be coated with at lithium titanate Form carbon coating on Ceng, obtain lithium titanate electrode plate；Wherein, the thickness of carbon coating is 13 microns；
5, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes that mass ratio is the nickle cobalt lithium manganate of 1:40:20, Kynoar binding agent and acetylene Black conductive agent, negative plate is above-mentioned lithium titanate electrode plate.It is assembled into lithium ion battery after winding, fluid injection, 0.3C electric current constant current constant voltage is used to be melted into 3.7V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity is protected Holdup is 98%.
Embodiment 4
Preparation lithium titanate electrode plate and lithium ion battery
1,100g Kynoar binding agent, 20g acetylene black conductor and 0.88kg lithium titanate are taken, uniformly It is dispersed in 200g N-Methyl pyrrolidone, disperses with the rotating speed high-speed stirred of 3000r/min, stir Obtain lithium titanate coating paste；
2, lithium titanate coating paste is coated on aluminium foil, dries under the conditions of 85 DEG C, aluminium foil is formed titanium Acid lithium coating, the thickness of lithium titanate coating is 100 microns；
3, the 380g that 18g Kynoar binding agent, 2g acetylene black conductor and mean diameter are 2 microns is taken Hard carbon, is dispersed in 400g N-Methyl pyrrolidone, disperses with the rotating speed high-speed stirred of 5000r/min, It is uniformly mixing to obtain carbon coating slurry；
4, carbon coating slurry is coated in lithium titanate coating, dries under the conditions of 90 DEG C, in lithium titanate coating Upper formation carbon coating, obtains lithium titanate electrode plate；Wherein, the thickness of carbon coating is 16 microns；
5, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes that mass ratio is the LiMn2O4 of 1:50:10, Kynoar binding agent and acetylene unlicensed tour guide Electricity agent, negative plate is above-mentioned lithium titanate electrode plate.After winding, fluid injection, it is assembled into lithium ion battery, makes With 0.4C electric current constant current constant voltage chemical conversion to 3.6V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity keeps Rate is 97%.
Embodiment 5
Preparation lithium titanate electrode plate and lithium ion battery
1, take 50g Kynoar binding agent, 10g acetylene black conductor and 0.94kg lithium titanate, uniformly divide It is dispersed in 2.1kg N-Methyl pyrrolidone, disperses with the rotating speed high-speed stirred of 4000r/min, stir To lithium titanate coating paste；
2, lithium titanate coating paste is coated on aluminium foil, dries under the conditions of 95 DEG C, aluminium foil is formed titanium Acid lithium coating, the thickness of lithium titanate coating is 120 microns；
3, the 600g that 30g Kynoar binding agent, 15g acetylene black conductor and mean diameter are 5 microns is taken Carbonaceous mesophase spherules, is dispersed in 600g N-Methyl pyrrolidone, with the rotating speed high speed of 4000r/min Dispersed with stirring, is uniformly mixing to obtain carbon coating slurry；
4, carbon coating slurry is coated in lithium titanate coating, dries under the conditions of 90 DEG C, in lithium titanate coating Upper formation carbon coating, obtains lithium titanate electrode plate；Wherein, the thickness of carbon coating is 15 microns；
5, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes nickel cobalt lithium aluminate, Kynoar binding agent and the acetylene that mass ratio is 1:50:10 Black conductive agent, negative plate is above-mentioned lithium titanate electrode plate.It is assembled into lithium ion battery after winding, fluid injection, 0.4C electric current constant current constant voltage is used to be melted into 3.6V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity is protected Holdup is 98%.
Embodiment 6
Preparation lithium titanate electrode plate and lithium ion battery
1,100g Kynoar binding agent, 100g acetylene black conductor and 0.8kg lithium titanate are taken, uniformly It is dispersed in 2.1kg N-Methyl pyrrolidone, disperses with the rotating speed high-speed stirred of 4000r/min, stir Obtain lithium titanate coating paste；
2, lithium titanate coating paste is coated on Copper Foil, dries under the conditions of 95 DEG C, Copper Foil is formed titanium Acid lithium coating, the thickness of lithium titanate coating is 120 microns；
3, take 20g Kynoar binding agent, 10g acetylene black conductor, 400g mean diameter are 3 microns Delanium and native graphite that 400g mean diameter is 3 microns, be dispersed in 800g N-methyl pyrrole In pyrrolidone, disperse with the rotating speed high-speed stirred of 4000r/min, be uniformly mixing to obtain carbon coating slurry；
4, carbon coating slurry is coated in lithium titanate coating, dries under the conditions of 90 DEG C, in lithium titanate coating Upper formation carbon coating, obtains lithium titanate electrode plate；Wherein, the thickness of carbon coating is 10 microns；
5, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes that mass ratio is the nickle cobalt lithium manganate of 1:50:10, Kynoar binding agent and acetylene Black conductive agent, negative plate is above-mentioned lithium titanate electrode plate.It is assembled into lithium ion battery after winding, fluid injection, 0.5C electric current constant current constant voltage is used to be melted into 3.6V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity is protected Holdup is 99%.
Embodiment 7
Preparation lithium titanate electrode plate and lithium ion battery
1, take 40g carboxymethyl cellulose binding agent, 60g butadiene-styrene rubber binding agent, 5g acetylene black conductor and 0.895kg lithium titanate, is dispersed in 2kg water, disperses with the rotating speed high-speed stirred of 4000r/min, stirs Mix and uniformly obtain lithium titanate coating paste；
2, lithium titanate coating paste is coated on Copper Foil, dries under the conditions of 80 DEG C, Copper Foil is formed titanium Acid lithium coating, the thickness of lithium titanate coating is 200 microns；
3,2g carboxymethyl cellulose binding agent, 2g butadiene-styrene rubber binding agent, 1g acetylene black conductor and 98g are taken Mean diameter is the hard carbon of 4 microns, is dispersed in 200g water, with the rotating speed high-speed stirring of 4000r/min Mix dispersion, be uniformly mixing to obtain carbon coating slurry；
4, carbon coating slurry is coated in lithium titanate coating, dries under the conditions of 80 DEG C, in lithium titanate coating Upper formation carbon coating, obtains lithium titanate electrode plate；Wherein, the thickness of carbon coating is 20 microns；
5, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes cobalt acid lithium, Kynoar binding agent and the acetylene unlicensed tour guide that mass ratio is 1:50:10 Electricity agent, negative plate is above-mentioned lithium titanate electrode plate.After winding, fluid injection, it is assembled into lithium ion battery, makes With 0.1C electric current constant current constant voltage chemical conversion to 3.9V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity keeps Rate is 98%.
Comparative example
Preparation lithium titanate electrode plate and lithium ion battery
1,100g Kynoar binding agent, 20g acetylene black conductor and 2kg lithium titanate are taken, dispersed In 2kg N-Methyl pyrrolidone, disperse with the rotating speed high-speed stirred of 3000r/min, be uniformly mixing to obtain titanium Acid lithium coating slurry；
2, lithium titanate coating paste is coated on Copper Foil, dries under the conditions of 90 DEG C, Copper Foil is formed titanium Acid lithium coating, obtains lithium titanate electrode plate；Wherein, the thickness of lithium titanate coating is 150 microns；
3, providing positive plate and negative plate, positive plate comprises aluminium foil and is laminated in positive-active layer on aluminium foil.Just The material of pole active layer includes that mass ratio is the LiMn2O4 of 1:50:10, Kynoar binding agent and acetylene unlicensed tour guide Electricity agent, negative plate is above-mentioned lithium titanate electrode plate.After winding, fluid injection, it is assembled into lithium ion battery, makes With 0.1C electric current constant current constant voltage chemical conversion to 3.9V, cut-off current 0.05C.After 1C circulates 500 weeks, capacity keeps Rate is 82%.
The lithium ion battery of embodiment 1 sees Fig. 2 with the cyclic curve contrast of the lithium ion battery of comparative example.By Fig. 2 can be seen that, the cycle performance of the lithium ion battery of embodiment 1 is better than following of the lithium ion battery of comparative example Ring performance.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended Claim is as the criterion.

Claims (8)

1. a lithium titanate electrode plate, it is characterised in that include collector, be laminated on described collector Lithium titanate coating and be laminated in the carbon coating in described lithium titanate coating, the material of described carbon coating includes carbon material Material, the first binding agent and the first conductive agent；
The thickness of described lithium titanate coating is 40 microns～200 microns；
The thickness of described carbon coating is 10 microns～20 microns；
The mean diameter of described material with carbon element is 500 nanometers～5 microns.
Lithium titanate electrode plate the most according to claim 1, it is characterised in that described material with carbon element is selected from people Make at least one in graphite, native graphite, soft carbon, carbonaceous mesophase spherules and hard carbon.
Lithium titanate electrode plate the most according to claim 1, it is characterised in that described first binding agent choosing At least one in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber, described first conductive agent is second Acetylene black.
Lithium titanate electrode plate the most according to claim 1, it is characterised in that described carbon coating presses quality Percentages:
Described material with carbon element accounts for 80%～98%；
Described first binding agent accounts for 0.5%～10%；And
Described first conductive agent accounts for 0.5～10%.
Lithium titanate electrode plate the most according to claim 1, it is characterised in that described lithium titanate coating Material includes lithium titanate, the second binding agent and the second conductive agent.
Lithium titanate electrode plate the most according to claim 5, it is characterised in that described second binding agent choosing At least one in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber, described second conductive agent is second Acetylene black.
Lithium titanate electrode plate the most according to claim 5, it is characterised in that described lithium titanate coating is pressed Mass percent:
Described lithium titanate accounts for 80%～98%；
Described second binding agent accounts for 0.5%～10%；And
Described second conductive agent accounts for 0.5～10%.
8. a lithium ion battery, the battery core including housing, being arranged in described housing and fill are in described shell Internal electrolyte, described battery core includes positive plate, barrier film and the negative plate stacked gradually, it is characterised in that Described negative plate is the lithium titanate electrode plate as described in any one of claim 1～7.
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CN105870400A (en) * 2015-01-20 2016-08-17 深圳市比克电池有限公司 Lithium ion battery negative pole piece, production method thereof, and lithium ion battery
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