CN106299331A - Based lithium-ion battery positive plate comprising lithium titanate coating and preparation method thereof and lithium ion battery - Google Patents
Based lithium-ion battery positive plate comprising lithium titanate coating and preparation method thereof and lithium ion battery Download PDFInfo
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- CN106299331A CN106299331A CN201510288550.2A CN201510288550A CN106299331A CN 106299331 A CN106299331 A CN 106299331A CN 201510288550 A CN201510288550 A CN 201510288550A CN 106299331 A CN106299331 A CN 106299331A
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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
- H01M4/36—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
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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
- 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
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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
- H01M4/139—Processes of manufacture
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 discloses a kind of based lithium-ion battery positive plate comprising lithium titanate coating and preparation method thereof and lithium ion battery, wherein, comprise the based lithium-ion battery positive plate of lithium titanate coating, the positive electrode material layer including collector, being formed at collection liquid surface and the lithium titanate coating being formed at positive electrode material layer surface, described lithium titanate coating layer thickness is 0.1-30 μm, and it is the lithium titanate of 80%-98%, the binding agent of 0.5%-10% and the conductive agent of 0.5%-10% that described lithium titanate coating comprises proportion；Technical solution of the present invention can improve lithium ion battery safety performance under ensureing lithium ion battery electrical property premise.
Description
Technical field
The present invention relates to lithium ion battery and manufacture field, particularly to a kind of lithium comprising lithium titanate coating from
Sub-battery anode slice and preparation method thereof and lithium ion battery.
Background technology
Lithium ion battery is a kind of novel green, high capacity power source, and it relies primarily on lithium ion at high oxidative
Reversible Cycle between positive pole and strong reducing property negative pole moves and realizes supplying power for outside；It possesses running voltage
Height, the advantages such as energy density is big, operating temperature range width, and charge and discharge platform is stable.
Lithium ion battery as high capacity power source in short circuit, overcharge, easily draw in the case of the abuse such as thermal shock
Thermal run away, causes cells burst or blast, and therefore to have become restriction lithium ion battery large-scale for safety problem
The major obstacle that change, energetic direction are developed.The main cause of lithium ion battery safety problem is internal short
Road is caused, i.e. the positive/negative plate of battery directly contacts.Therefore in the energy density not reducing battery
On the premise of, reduce the severe degree of reaction between positive pole and negative pole, become guarantee lithium ion battery electrical
The main path of its security performance is improved under energy premise.
Summary of the invention
The main object of the present invention is to provide a kind of based lithium-ion battery positive plate comprising lithium titanate coating, purport
Under ensureing lithium ion battery electrical property premise, improve its security performance.
For achieving the above object, the based lithium-ion battery positive plate comprising lithium titanate coating that the present invention proposes,
The positive electrode material layer including collector, being formed at collection liquid surface and the titanium being formed at positive electrode material layer surface
Acid lithium coating.
Preferably, described lithium titanate coating layer thickness is 0.1-30 μm, and described lithium titanate coating comprises proportion and is
The lithium titanate of 80%-98%, the binding agent of 0.5%-10% and the conductive agent of 0.5%-10%.
Preferably, described lithium titanate coating layer thickness is 2-6 μm, and described lithium titanate coating comprises proportion and is
The lithium titanate of 87%-93%, the binding agent of 4%-10% and the conductive agent of 3%-7%.
Preferably, described lithium titanate be pure lithium titanate, through lithium titanate or the metal of cladding and nonmetal mix
The lithium titanate of miscellaneous modification；Described binding agent is PVDF, PVDF-HFP, SBR, CMC, PVA, PMMA,
At least one in PAN and gelatin；Described conductive agent is that graphite, acetylene black, gas-phase carbon fiber, carbon are received
At least one in mitron and Graphene.
Preferably, described positive electrode material layer comprises proportion is the positive electrode of 80%-98%, 0.5%-10%
Binding agent and the conductive agent of 0.5%-10%；Described positive electrode is cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary
Material, nickel cobalt binary material, LiFePO4, lithium manganese phosphate, rich lithium manganese base solid solution and nickel manganese binary material
In material at least one；Described binding agent is PVDF, PVDF-HFP, SBR, CMC, PVA, PMMA,
At least one in PAN and gelatin；Described conductive agent is graphite, acetylene black, gas-phase carbon fiber, carbon nanometer
At least one in pipe and Graphene.
Preferably, described collector is provided with lug, described collector be aluminium foil/net, stainless steel foil/net,
Copper Foil/net or nickel plating Copper Foil/net, described collector thickness is between 5 μm-50 μm；Described lug is aluminum
Lug, nickel lug, copper nickel composite band or copper nickel plating lug, described lug thickness is at 0.06mm-0.6mm
Between.
The present invention also provides for the preparation side of a kind of above-mentioned based lithium-ion battery positive plate comprising lithium titanate coating
Method, including:
Form positive electrode material layer in collection liquid surface coating, prepare battery anode slice；
Lithium titanate, binding agent and conductive agent are added in solvent by the content ratio in described lithium titanate coating,
Stir prepared lithium titanate slurry；
On the surface of the positive electrode material layer that lithium titanate slurry is uniformly coated to battery anode slice, after drying,
Prepare the based lithium-ion battery positive plate comprising lithium titanate coating, be coated to positive electrode material layer at lithium titanate slurry
Surface before and/or lithium titanate slurry be coated to positive electrode material layer surface and dry after, to battery
Positive plate carries out roll-in.
Preferably, described at collection liquid surface coating formation positive electrode material layer, prepare the step of battery anode slice
Suddenly specifically include: by positive electrode, binding agent and conductive agent according to the content ratio of described positive electrode material layer
Adding in solvent, stir prepared anode sizing agent；Anode sizing agent is coated uniformly on collection liquid surface,
After drying, form positive electrode material layer at collection liquid surface.
Preferably, described by positive electrode, binding agent and conductive agent according to the content of described positive electrode material layer
Ratio adds in solvent, and the step of the prepared anode sizing agent that stirs specifically includes: by positive electrode, glue
Knot agent and conductive agent add in solvent according to the content ratio of described positive electrode material layer, in double-planet stirring point
Dissipate in machine with revolution 5-50r/min, rotation 400-5000r/min mixing speed under stir to prepare and stir
Uniformly prepare anode sizing agent；
Described anode sizing agent is coated uniformly on collection liquid surface, after drying, is just formed at collection liquid surface
In the step of pole material layer, dry temperature and be 80-120 DEG C；
Described that lithium titanate, binding agent and conductive agent is molten by the content ratio addition in described lithium titanate coating
In agent, the step of the prepared lithium titanate slurry that stirs specifically includes: by lithium titanate, binding agent and conduction
Agent adds in solvent by the content ratio in described lithium titanate coating, by public affairs in double-planet stirring dispersion machine
Turn the prepared lithium titanate slurry that stirs under the mixing speed of 5-50r/min, rotation 400-5000r/min；
On the surface of the described positive electrode material layer that lithium titanate slurry is uniformly coated to battery anode slice, dry
After, preparing in the step of the based lithium-ion battery positive plate comprising lithium titanate coating, drying temperature is 80-120
℃；
Described before lithium titanate slurry is coated to the surface of positive electrode material layer and/or in the coating of lithium titanate slurry
After the surface and drying of positive electrode material layer, battery anode slice is carried out in the step of roll-in, described roller
The compacted density of pressure is at 2-4.5g/cm3Between.
The present invention also provides for a kind of lithium ion battery, including the above-mentioned lithium-ion electric comprising lithium titanate coating
Pond positive plate.
Technical solution of the present invention, by forming one layer of lithium titanate coating in positive electrode material layer surface-coated, utilizes
The security performance of lithium titanate material is good, lithium ion diffusion coefficient high, and in charge and discharge process, volume does not becomes
Change and the features such as current potential is low, oxidisability is little under charged state, improve lithium ion battery security and electricity
Performance；The lithium ion battery being assembled into by the electrode film comprising lithium titanate coating not only internal resistance is little, multiplying power
Performance is good, and self discharge is little, and security performance is high and has extended cycle life.
Accompanying drawing explanation
Fig. 1 is the cross-sectional view that the present invention comprises the based lithium-ion battery positive plate of lithium titanate coating；
Fig. 2 is the flow chart that the present invention comprises the preparation method of the based lithium-ion battery positive plate of lithium titanate coating；
Fig. 3 is the lithium ion battery embodiment 1 short-circuit skin temperature profile figure with comparative example 1 of the present invention；
Fig. 4 be lithium ion battery embodiment 1 and the comparative example 1 of the present invention overcharge skin temperature profile figure；
Fig. 5 is the lithium ion battery embodiment 1 box traction substation with the self discharge K value of comparative example 1 of the present invention；
Fig. 6 is the lithium ion battery embodiment 1 cycle life curve comparison figure with comparative example 1 of the present invention.
Drawing reference numeral illustrates:
| Collector 20 | Positive electrode material layer 40 | Lithium titanate coating 60 |
The realization of the object of the invention, functional characteristics and advantage will in conjunction with the embodiments, do referring to the drawings further
Explanation.
Detailed description of the invention
Below in conjunction with the accompanying drawings and specific embodiment is described further with regard to technical scheme.Should
Understanding, specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The present invention proposes a kind of based lithium-ion battery positive plate comprising lithium titanate coating.
It is the cross-section structure that the present invention comprises the based lithium-ion battery positive plate of lithium titanate coating with reference to Fig. 1, Fig. 1
Schematic diagram.
In the present invention, this based lithium-ion battery positive plate comprising lithium titanate coating includes collector 20, shape
The positive electrode material layer 40 becoming collector 20 surface and the lithium titanate being formed at positive electrode material layer 40 surface are coated with
Layer 60.
Owing to lithium titanate is zero strain material, good cycle, lithium ion diffusion coefficient are high, to lithium current potential
Higher, security performance good, therefore, little as coating material not only internal resistance, has electro-chemical activity
(theoretical gram volume is 175mAh/g), and the extent of reaction between positive/negative plate can be reduced, strengthen
The safety of lithium ion battery；Proper amount of conductive agent joined by lithium titanate and bonding is coated on positive electrode material layer 40
Surface forms lithium titanate coating 60, and owing to effect and the positive electrode expansion rate of binding agent are little, lithium titanate is coated with
Layer 60 difficult drop-off；The lithium titanate coating 60 of Rational Thickness is arranged on high oxidative positive material material and bears
Between pole, add one layer of cushion, greatly improve the safety of lithium ion battery, reduce simultaneously
Self-discharge rate.
Described lithium titanate coating 60 thickness is 0.1-30 μm, and described lithium titanate coating 60 comprises proportion and is
The lithium titanate of 80%-98%, the binding agent of 0.5%-10% and the conductive agent of 0.5%-10%；Preferably, described
It is the lithium titanate of 87%-93%, the binding agent of 4%-10% and 3%-7% that lithium titanate coating 60 comprises proportion
Conductive agent.By being rationally selected to reach preferable to binding agent, conductive agent and lithium titanate content
Bonding effect, electrical property and buffering effect；Preferably, lithium titanate coating described in the present embodiment 60 is thick
Degree is 2-6 μm.Lithium titanate coating 60 thickness arranges the thinnest to reach good buffering effect, if
Put to obtain the thickest then reduction positive plate compacted density and the capacity of battery.
Further, in the present embodiment, described lithium titanate can be pure lithium titanate, through carbon, metal oxygen
Compound (Al2O3、ZrO2、TiO2, MgO, ZnO etc.), metal phosphate (FePO3、AlPO3
Deng) lithium titanate that is coated with or metallic element (Mg, Al, Fe, Zr, Cr, Ni, Cu, La etc.) and non-
The lithium titanate of metallic element (F, N, P, S, C etc.) doping vario-property；Use described binding agent for for
Lithium titanate coating 60 provides adhesive property, and it can be that (polyvinylidene fluoride gathers partially PVDF
Fluorothene), PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride
Alkene-hexafluoropropene), SBR (styrene butadiene rubber, butadiene-styrene rubber rubber), CMC (sodium
Salt of caboxy methyl cellulose, sodium carboxymethyl cellulose), PVA ((polyvinyl alcohol,
Polyvinyl alcohol), PMMA (polymethyl methacrylate, polymethyl methacrylate), PAN
At least one in (polyacrylonitrile, polyacrylonitrile) and gelatin, it is preferred that described binding agent is
PVDF；Described conductive agent for regulating the electric conductivity of described lithium titanate coating 60, its can be graphite,
At least one in acetylene black, gas-phase carbon fiber, CNT and Graphene, it is preferable that described conduction
Agent is acetylene black.
Further, described positive electrode material layer 40 comprise positive electrode that proportion is 80%-98%,
The binding agent of 0.5%-10% and the conductive agent of 0.5%-10%；Described positive electrode be cobalt acid lithium, LiMn2O4,
Nickel-cobalt-manganese ternary material, nickel cobalt binary material, LiFePO4, lithium manganese phosphate, rich lithium manganese base solid solution and
In nickel manganese binary material at least one；Described binding agent is PVDF, PVDF-HFP, SBR, CMC,
At least one in PVA, PMMA, PAN and gelatin；Described conductive agent is graphite, acetylene black, gas phase
At least one in carbon fiber, CNT and Graphene.The positive electrode of described positive electrode material layer 40 is
The active substance of positive pole, binding agent is for ensureing the adhesive property of positive electrode material layer 40, and conductive agent is used for adjusting
Save the electric conductivity of described positive electrode material layer 40, can by the preferred described positive electrode material layer 40 of content
Reach preferably bonding effect and electrical property.
The function of described collector 20 is mainly collected by the electric current that cell active materials produces so that shape
The current versus becoming bigger exports, and therefore collector 20 should be fully contacted with active substance, and internal resistance should
The least it is preferred, lug derived current can be set, and the material and thickness to collector 20 is fitted
When selection.Therefore, further, described collector 20 is provided with lug, and described collector 20 is
Aluminium foil/net, stainless steel foil/net, Copper Foil/net or nickel plating Copper Foil/net, described collector 20 thickness is in 5 μm-50
Between μm；Described lug is aluminium pole ears, nickel lug, copper nickel composite band or copper nickel plating lug, described pole
Ear thickness is between 0.06mm-0.6mm.
Further combined with Fig. 1 and Fig. 2, the present invention also proposes a kind of above-mentioned lithium ion comprising lithium titanate coating
The preparation method of battery anode slice, including:
Step S10；Form positive electrode material layer 40 in collector 20 surface-coated, prepare battery anode slice.
Wherein positive electrode material layer 40 is formed on positive and negative two surfaces of collector 20, in this step,
Positive electrode, binding agent and conductive agent are added in solvent according to the content ratio of above-mentioned positive electrode material layer 40,
Stir prepared anode sizing agent；Anode sizing agent is coated uniformly on collector 20 surface, after drying,
Collector 20 surface forms positive electrode material layer 40；Wherein, described solvent can be N-Methyl pyrrolidone,
In dimethyl sulfoxide, acetone, butanone, Ketohexamethylene, ethanol, propylene glycol, water and toluene at least one
Kind；Anode sizing agent be coated uniformly on collector 20 surface dry time, dry temperature be 80-120 DEG C,
Actual temp rationally selects according to the character of solvent.
In practical operation, anode sizing agent can be completed by technique in detail below and prepare；By positive electrode,
Binding agent and conductive agent add in solvent according to the content ratio of described positive electrode material layer 40, stir at double-planet
Mix in dispersion machine with revolution 5-50r/min, rotation 400-5000r/min mixing speed under stir prepared
Stir prepared anode sizing agent.
Step S20；By lithium titanate, binding agent and conductive agent by the content ratio in described lithium titanate coating 60
Example adds in solvent, and stir prepared lithium titanate slurry.
In this step, prepare lithium titanate slurry by the lithium titanate of rational proportion, binding agent and conductive agent,
On the surface of positive electrode material layer 40, coating forms lithium titanate coating 60, and practical operation can be by following technique
Carry out, lithium titanate, binding agent and conductive agent are added molten by the content ratio in described lithium titanate coating 60
In agent, by revolution 5-50r/min, the stirring speed of rotation 400-5000r/min in double-planet stirring dispersion machine
Stir under degree prepared lithium titanate slurry；Wherein, described solvent can be N-Methyl pyrrolidone, two
At least one in methyl sulfoxide, acetone, butanone, Ketohexamethylene, ethanol, propylene glycol, water and toluene.
Step S30；Lithium titanate slurry is uniformly coated to the surface of the positive electrode material layer 40 of battery anode slice
On, after drying, prepare the based lithium-ion battery positive plate comprising lithium titanate coating 60, be coated with at lithium titanate slurry
The surface of positive electrode material layer before being layed onto the surface of positive electrode material layer 40 and/or it is coated at lithium titanate slurry
And after drying, battery anode slice is carried out roll-in.
In this step, the surface of the positive electrode material layer that lithium titanate slurry is uniformly coated to battery anode slice is laggard
When row is dried, drying temperature and be 80-120 DEG C, actual temp rationally selects according to the character of solvent；
So that positive electrode and collector 20 are fitted tightr, need to carry out roll-in, can be at coating metatitanic acid
Roll-in or roll-in after lithium titanate coated coating 60 is carried out, it is also possible at coating titanium before lithium coating 60
All carrying out roll-in before and after acid lithium coating 60, roll-in is also beneficial to lithium titanate coating 60 and positive pole material
The bed of material 40 is fitted effect.Concrete operations can be the battery after lithium titanate slurry is uniformly coated to roll-in just
On the surface of the positive electrode material layer 40 of pole piece, after drying, roll-in or not roll-in prepare and comprise lithium titanate again
The based lithium-ion battery positive plate of coating 60；Or lithium titanate slurry is just uniformly being coated to the battery of non-roll-in
On the surface of the positive electrode material layer 40 of pole piece, dry back roller suppress to comprise the lithium of lithium titanate coating 60 from
Sub-battery anode slice.
Wherein, the compacted density of described roll-in is at 2-4.5g/cm3Between.By controlling compacted density, it is possible to
Well ensure the bond effect that collector 20, positive electrode material layer 40, lithium titanate coating 60 are mutual, prevent
Positive electrode material layer 40 or lithium titanate coating 60 peel off dry linting, promote the reliability of positive plate.
Further, the preparation method of the based lithium-ion battery positive plate comprising lithium titanate coating described in is all right
Including: step S40；By on described tab welding to described collector 20.
The present invention also provides for a kind of lithium ion battery, including the above-mentioned lithium-ion electric comprising lithium titanate coating
Pond positive plate.
Hereby the embodiment of the present invention is described in detail as follows, but the present invention is not limited to scope of embodiments.
Embodiment 1；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg cobalt acid lithium, add N-first
In base ketopyrrolidine, disperse just preparing with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min
Pole slurry, is coated on anode sizing agent on aluminium foil, dries and obtain battery anode slice under the conditions of 80～120 DEG C；
Then take 15g Kynoar binding agent, 10g acetylene black conductor and 200g lithium titanate, add N-first
In base ketopyrrolidine, after being uniformly dispersed with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min,
It is coated uniformly on cobalt acid lithium layer surface, dries under the conditions of 80～120 DEG C, after to roller, at aluminium foil
Upper soldering polar ear i.e. obtains the based lithium-ion battery positive plate comprising lithium titanate coating of embodiment 1, is compacted close
Degree is 3.9g/cm3, coating layer thickness is about 3 microns.The lithium comprising lithium titanate coating of described embodiment 1 from
Sub-battery anode slice is assembled into the lithium ion battery of embodiment 1 after winding, fluid injection.
Comparative example 1；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg cobalt acid lithium, add N-first
In base ketopyrrolidine, disperse with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min, will system
The slurry obtained is coated on aluminium foil, dries under the conditions of 80～120 DEG C, after to roller, welds on aluminium foil
Connecing lug and obtain based lithium-ion battery positive plate, compacted density is 3.9g/cm3.The lithium of described comparative example 1 from
Sub-battery anode slice is assembled into the lithium ion battery of comparative example 1 after winding, fluid injection.
Embodiment 2；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg cobalt acid lithium, add N-first
In base ketopyrrolidine, disperse just preparing with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min
Pole slurry, is coated on anode sizing agent on aluminium foil, dries and obtain battery anode slice under the conditions of 80～120 DEG C；
Carrying out roller to the battery anode slice after drying, compacted density controls at 3.9g/cm3；Then 15g is taken poly-partially
Fluorothene binding agent, 10g acetylene black conductor and 200g lithium titanate, add in N-Methyl pyrrolidone,
After being uniformly dispersed with revolution 30r/min, the rotating speed high-speed stirred of rotation 2500r/min, it is coated uniformly on cobalt
On acid lithium layer surface, drying under the conditions of 80～120 DEG C, on aluminium foil, soldering polar ear i.e. obtains embodiment 2
The based lithium-ion battery positive plate comprising lithium titanate coating, coating layer thickness is about 3 microns.Described embodiment 2
The based lithium-ion battery positive plate comprising lithium titanate coating through winding, be assembled into embodiment 2 after fluid injection
Lithium ion battery.
Embodiment 3；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg ternary material, add N-
In methyl pyrrolidone, disperse to prepare with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 3000r/min
Anode sizing agent, is coated on anode sizing agent on aluminium foil, dries and obtain anode under the conditions of 80～120 DEG C
Sheet；Then take 15g Kynoar binding agent, 10g acetylene black conductor and 200g lithium titanate, add
In N-Methyl pyrrolidone, disperse all with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min
After even, it is coated uniformly on ternary material layer surface, dries under the conditions of 80～130 DEG C, after to roller,
On aluminium foil, soldering polar ear i.e. obtains the based lithium-ion battery positive plate comprising lithium titanate coating of embodiment 3,
Compacted density is 3.3g/cm3, coating layer thickness is about 4 microns.Described embodiment 3 comprise lithium titanate coating
Based lithium-ion battery positive plate through winding, the lithium ion battery that is assembled into embodiment 3 after fluid injection.
Embodiment 4；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg ternary material, add N-
In methyl pyrrolidone, disperse to prepare with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 3000r/min
Anode sizing agent, is coated on anode sizing agent on aluminium foil, dries and obtain anode under the conditions of 80～120 DEG C
Sheet；Becoming to carry out roller to the battery anode slice after drying half, compacted density controls at 3.4g/cm3；Then take
15g Kynoar binding agent, 10g acetylene black conductor and 200g lithium titanate, add N-methylpyrrole
In alkanone, after being uniformly dispersed with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min, uniformly
It is coated on ternary material layer surface, dries under the conditions of 80～130 DEG C, soldering polar ear and get final product on aluminium foil
To the based lithium-ion battery positive plate comprising lithium titanate coating of embodiment 4, coating layer thickness is about 4 microns.
The based lithium-ion battery positive plate comprising lithium titanate coating of described embodiment 4 assembles after winding, fluid injection
Become the lithium ion battery of embodiment 4.
Embodiment 5；
Take 100g Kynoar binding agent, 20g acetylene black conductor and 2kg LiMn2O4, add N-first
In base ketopyrrolidine, disperse just preparing with the rotating speed high-speed stirred of the 20r/min that revolves round the sun, rotation 3000r/min
Pole slurry, is coated on anode sizing agent on aluminium foil, dries and obtain battery anode slice under the conditions of 80～120 DEG C；
Then 15g Kynoar binding agent, 10g acetylene black conductor and 200g lithium titanate are taken, dispersed
In N-Methyl pyrrolidone, after high-speed stirred dispersion, it is coated uniformly on mangaic acid lithium layer surface,
Drying under the conditions of 80～110 DEG C, after to roller, on aluminium foil, soldering polar ear i.e. obtains the bag of embodiment 5
Containing the based lithium-ion battery positive plate of metatitanic acid lithium coating, coating layer thickness is about 2 microns.Described embodiment 5
The based lithium-ion battery positive plate comprising lithium titanate coating is assembled into the lithium of embodiment 5 after winding, fluid injection
Ion battery.
Embodiment 6；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg cobalt acid lithium, add N-first
In base ketopyrrolidine, disperse just preparing with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min
Pole slurry, is coated on anode sizing agent on aluminium foil, dries and obtain battery anode slice under the conditions of 80～120 DEG C；
Carrying out roller to the battery anode slice after drying, compacted density controls at 3.9g/cm3；Then 11g is taken poly-partially
Fluorothene and 4gPVA binding agent, 15g carbon nanotube conducting agent and 200gAl3+Doped lithium titanate, adds
In the mixed solvent of second alcohol and water, divide with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min
After dissipating uniformly, it is coated uniformly on cobalt acid lithium layer surface, dries under the conditions of 80～120 DEG C, on aluminium foil
Soldering polar ear i.e. obtains the based lithium-ion battery positive plate comprising lithium titanate coating of embodiment 6, coating layer thickness
It is about 3.5 microns.Described embodiment 6 comprise the based lithium-ion battery positive plate of lithium titanate coating through winding,
The lithium ion battery of embodiment 6 it is assembled into after fluid injection.
Embodiment 7；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg cobalt acid lithium, add N-first
In base ketopyrrolidine, disperse just preparing with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min
Pole slurry, is coated on anode sizing agent on aluminium foil, dries and obtain battery anode slice under the conditions of 80～120 DEG C；
Then take 6g gelatin binder, 4g graphene conductive agent is coated with lithium titanate with 200g carbon, adds N-methyl
In the mixed solvent of ketopyrrolidine and acetone, with the 30r/min that revolves round the sun, the rotating speed high speed of rotation 2500r/min
After dispersed with stirring is uniform, it is coated uniformly on cobalt acid lithium layer surface, dries under the conditions of 80～120 DEG C, so
After carry out roller, compacted density is 3.85g/cm3, lithium titanate coating layer thickness is 2.5 microns, on aluminium foil
Soldering polar ear i.e. obtains the based lithium-ion battery positive plate comprising lithium titanate coating of embodiment 7.Described enforcement
The based lithium-ion battery positive plate comprising lithium titanate coating of example 7 is assembled into embodiment 7 after winding, fluid injection
Lithium ion battery.
Embodiment 8；
Take 42g Kynoar binding agent, 50g acetylene black conductor and 2kg cobalt acid lithium, add N-first
In base ketopyrrolidine, disperse just preparing with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min
Pole slurry, is coated on anode sizing agent on stainless (steel) wire, dries and just obtaining battery under the conditions of 80～120 DEG C
Pole piece；Carrying out roller to the battery anode slice after drying, compacted density controls at 3.9g/cm3；Then take
8g Kynoar binding agent, 8g CNT electricity agent and 200g lithium titanate, add N-crassitude
In ketone, after being uniformly dispersed with the rotating speed high-speed stirred of the 30r/min that revolves round the sun, rotation 2500r/min, uniformly it is coated with
Overlay on cobalt acid lithium layer surface, dry under the conditions of 80～120 DEG C, soldering polar ear and get final product on stainless (steel) wire
To the based lithium-ion battery positive plate comprising lithium titanate coating of embodiment 8, coating layer thickness is about 3.3 microns.
The based lithium-ion battery positive plate comprising lithium titanate coating of described embodiment 8 assembles after winding, fluid injection
Become the lithium ion battery of embodiment 8.
The safety according to GB/T 18287-2000, above-mentioned lithium ion battery is tested battery short circuit, overcharging
Can, K value and capability retention, wherein over-charging of battery test overcharges test for 3C/4.8V；K value is unit
The voltage drop of the battery in the time；Capability retention is the capability retention after 1C circulates 500 weeks.Test
Result is as shown in table 1.
Table 1
Meanwhile, referring to Fig. 3 to 6, the conventional pole piece indicated in figure is the lithium-ion electric of comparative example 1 preparation
Pond positive plate；In figure indicate the lithium coating pole piece containing metatitanic acid be embodiment 1 preparation containing metatitanic acid lithium coating
Based lithium-ion battery positive plate.Fig. 3 is lithium ion battery and the lithium ion battery of embodiment 1 of comparative example 1
The lithium ion battery that positive plate assembles carries out short-circuit test according to GB/T 18287-2000, the short-circuit table obtained
Surface temperature curve chart；Fig. 4 is lithium ion battery and the lithium ion battery of embodiment 1 preparation of comparative example 1
Carrying out 3C/4.8V according to GB/T 18287-2000 and overcharge test, obtain overcharges skin temperature profile figure；
Fig. 5 is the lithium ion battery of comparative example 1 and the lithium ion battery of embodiment 1 carries out the test of K value, obtains
The box traction substation of self discharge K value；Lithium ion battery that Fig. 6 is prepared for comparative example 1 and embodiment 1
Lithium ion battery is circulated life test, the cycle life curve comparison figure obtained.
By the test data of table 1 and Fig. 3 to Fig. 6 it is recognised that and the lithium that assembles of conventional positive plate from
Sub-battery is compared, the lithium ion battery that the based lithium-ion battery positive plate containing metatitanic acid lithium coating of the present invention assembles,
Overcharge, short circuit time surface temperature rise slowly, and temperature is relatively low, and security performance significantly improves；And from certainly
Electric discharge K value is relatively low, battery capacity conservation rate high, is conducive to extending the service life of lithium ion battery.
It should be noted that, the technical scheme of each embodiment of the present invention can be combined with each other, but must
Must be based on those skilled in the art is capable of, when the combination of technical scheme occurs conflicting
People should think that the combination of this technical scheme does not exists, the most not at application claims when maybe cannot realize
Within protection domain.
The foregoing is only the preferred embodiments of the present invention, not thereby limit the scope of the claims of the present invention,
Every equivalent structure transformation utilizing description of the invention and accompanying drawing content to be made, or directly or indirectly use
In the technical field that other are relevant, the most in like manner it is included in the scope of patent protection of the present invention.
Claims (10)
1. the based lithium-ion battery positive plate comprising lithium titanate coating, it is characterised in that include afflux
Body, it is formed at the positive electrode material layer of collection liquid surface and is formed at the lithium titanate coating on positive electrode material layer surface.
Comprising the based lithium-ion battery positive plate of lithium titanate coating the most as claimed in claim 1, its feature exists
In, described lithium titanate coating layer thickness is 0.1-30 μm, and it is 80%-98% that described lithium titanate coating comprises proportion
Lithium titanate, the binding agent of 0.5%-10% and the conductive agent of 0.5%-10%.
Comprise the based lithium-ion battery positive plate of lithium titanate coating the most as claimed in claim 2, its feature
Being, described lithium titanate coating layer thickness is 2-6 μm, and it is 87%-93% that described lithium titanate coating comprises proportion
Lithium titanate, the binding agent of 4%-10% and the conductive agent of 3%-7%.
4. the lithium ion cell positive comprising lithium titanate coating as according to any one of Claims 2 or 3
Sheet, it is characterised in that described lithium titanate be pure lithium titanate, through cladding process lithium titanate or metal and
The lithium titanate that nonmetal doping is modified；Described binding agent is PVDF, PVDF-HFP, SBR, CMC,
At least one in PVA, PMMA, PAN and gelatin；Described conductive agent is graphite, acetylene black, gas
At least one in phase carbon fiber, CNT and Graphene.
Comprising the based lithium-ion battery positive plate of lithium titanate coating the most as claimed in claim 1, its feature exists
In, described positive electrode material layer comprise proportion be the positive electrode of 80%-98%, the binding agent of 0.5%-10% and
The conductive agent of 0.5%-10%；Described positive electrode is cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material, nickel
In cobalt binary material, LiFePO4, lithium manganese phosphate, rich lithium manganese base solid solution and nickel manganese binary material at least
A kind of；Described binding agent is PVDF, PVDF-HFP, SBR, CMC, PVA, PMMA, PAN
With at least one in gelatin；Described conductive agent be graphite, acetylene black, gas-phase carbon fiber, CNT and
At least one in Graphene.
Comprising the based lithium-ion battery positive plate of lithium titanate coating the most as claimed in claim 5, its feature exists
In, described collector is provided with lug, described collector be aluminium foil/net, stainless steel foil/net, Copper Foil/net or
Nickel plating Copper Foil/net, described collector thickness is between 5 μm-50 μm；Described lug is aluminium pole ears, nickel
Lug, copper nickel composite band or copper nickel plating lug, described lug thickness is between 0.06mm-0.6mm.
7. one kind is just comprising the lithium ion battery of lithium titanate coating as according to any one of claim 1 to 6
The preparation method of pole piece, it is characterised in that including:
Form positive electrode material layer in collection liquid surface coating, prepare battery anode slice；
Lithium titanate, binding agent and conductive agent are added in solvent by the content ratio in described lithium titanate coating,
Stir prepared lithium titanate slurry；
On the surface of the positive electrode material layer that lithium titanate slurry is uniformly coated to battery anode slice, after drying,
Prepare the based lithium-ion battery positive plate comprising lithium titanate coating, be coated to positive electrode material layer at lithium titanate slurry
Surface before and/or lithium titanate slurry be coated to positive electrode material layer surface and dry after, to battery
Positive plate carries out roll-in.
Comprise the preparation method of the based lithium-ion battery positive plate of lithium titanate coating the most as claimed in claim 7,
It is characterized in that:
Described at collection liquid surface coating formation positive electrode material layer, the step preparing battery anode slice is specifically wrapped
Include: by positive electrode, binding agent and conductive agent according to the content of positive electrode material layer described in claim 5
Ratio adds in solvent, and stir prepared anode sizing agent；Anode sizing agent is coated uniformly on afflux body surface
Face, after drying, forms positive electrode material layer at collection liquid surface.
Comprise the preparation method of the based lithium-ion battery positive plate of lithium titanate coating the most as claimed in claim 8,
It is characterized in that:
Described by positive electrode, binding agent and conductive agent according to described positive electrode material layer content ratio add
In solvent, the step of the prepared anode sizing agent that stirs specifically includes: by positive electrode, binding agent with lead
Electricity agent adds in solvent according to the content ratio of described positive electrode material layer, uses in double-planet stirring dispersion machine
Revolution 5-50r/min, rotation 400-5000r/min mixing speed under stir prepare stir prepared
Anode sizing agent；
Described anode sizing agent is coated uniformly on collection liquid surface, after drying, is just formed at collection liquid surface
In the step of pole material layer, dry temperature and be 80-120 DEG C；
Described that lithium titanate, binding agent and conductive agent is molten by the content ratio addition in described lithium titanate coating
In agent, the step of the prepared lithium titanate slurry that stirs specifically includes: by lithium titanate, binding agent and conduction
Agent adds in solvent by the content ratio in described lithium titanate coating, by public affairs in double-planet stirring dispersion machine
Turn the prepared lithium titanate slurry that stirs under the mixing speed of 5-50r/min, rotation 400-5000r/min；
On the surface of the described positive electrode material layer that lithium titanate slurry is uniformly coated to battery anode slice, dry
After, preparing in the step of the based lithium-ion battery positive plate comprising lithium titanate coating, drying temperature is 80-120
℃；
Described before lithium titanate slurry is coated to the surface of positive electrode material layer and/or in the coating of lithium titanate slurry
After the surface and drying of positive electrode material layer, battery anode slice is carried out in the step of roll-in, described roller
The compacted density of pressure is at 2-4.5g/cm3Between.
10. a lithium ion battery, it is characterised in that include comprising metatitanic acid as described in claim 1-6
The based lithium-ion battery positive plate of lithium coating.
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| CN110752350A (en) * | 2019-11-02 | 2020-02-04 | 河南电池研究院有限公司 | Preparation method of soft package lithium ion battery positive electrode functional coating for relieving deposition of metal ions on negative electrode |
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