CN101174684B - Battery anode and lithium ion battery using the same and their production method - Google Patents
Battery anode and lithium ion battery using the same and their production method Download PDFInfo
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- CN101174684B CN101174684B CN2006101385011A CN200610138501A CN101174684B CN 101174684 B CN101174684 B CN 101174684B CN 2006101385011 A CN2006101385011 A CN 2006101385011A CN 200610138501 A CN200610138501 A CN 200610138501A CN 101174684 B CN101174684 B CN 101174684B
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- 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 battery anode, which comprises a collecting body and an anode material coating layer that is coated on the collecting body, the anode material comprises an anode active substance, a conducting agent and an adhesion agent, wherein, the anode also comprises a second coating layer, the second coating layer is coated on the surface of the anode material coating layer, the second coating layer comprises metal oxide, anode active substance, a conducting agent and an adhesion agent; the metal oxide is one or more of the metal oxide in the IIA group, the IIIA group,the IVA group, the IIB group, the IIIB group and the IVB group. The battery prepared with the anode of the present invention has good storage performance and good cycling performance; especially under the condition of high temperature, the advantages of the battery prepared by the present invention on the aspect of the storage performance and the cycling performance are more obvious.
Description
Technical field
The invention relates to a kind of anode and use this anodal battery and their preparation method, more specifically say so about a kind of anode and this anodal lithium ion battery of employing and their preparation method.
Background technology
Lithium ion battery mainly comprises the pole piece and the nonaqueous electrolytic solution that are sealed in the battery container as a kind of chemical power source.Wherein, pole piece comprises battery electrode and barrier film.Battery electrode is divided into positive pole and negative pole again.Positive and negative electrode contains the positive active material and the negative electrode active material that can reversibly embed and disengage lithium ion respectively.Positive active material is mainly the composition metal acidulants that lithium cobalt oxygen, lithium nickel oxygen and lithium manganese oxygen etc. can disengage and embed the lithium of lithium ion; Negative electrode active material is mainly the material with carbon element that can embed and disengage lithium ion equally with layer structure, as graphite.
Lithium ion battery is when charging, and lithium ion disengages from the interlayer of positive active material, arrives negative plate by barrier film between the positive/negative plate and electrolyte, embeds the interlayer of the negative electrode active material with layer structure; Otherwise during discharge.In carrying out above-mentioned charge and discharge cycles process or storage process, all there is capacity attenuation in various degree in lithium ion battery, especially the capacity attenuation under the hot environment is even more serious, thereby causes the storge quality of lithium ion battery and the requirement that cycle performance can't meet anticipation.
By discovering, the relatively poor main cause of lithium ion battery storge quality and cycle performance be positive active material easily and electrolyte react, thereby make the performance of positive active material that variation take place.
Current, for the storge quality that improves battery and the problem of cycle performance difference, a large amount of research has been arranged to being applied to the positive active material in the lithium ion battery, to prevent the reaction of positive active material and electrolyte.
For example, US2003148182 and CN1459131A suppress the reaction of positive active material and electrolyte, thereby improve the storge quality under cycle performance of battery and the high temperature by at positive active material surface clad oxide.But, chemical packs coating process complexity, manufacturing cycle is long, and the cost height need carry out long high temperature sintering to coating and just can obtain coating layer or the constitutionally stable composite metal oxide that mixes the lithium that other metal is arranged.
In addition, JP2001238692A is by adding lithium carbonate in positive active material, suppressing reaction anodal and electrolyte.But the adding of lithium carbonate can not form the protective layer of one deck densification on the positive active material surface, and positive active material still can react with electrolyte, and the adding of lithium carbonate also can reduce battery capacity.
Therefore, CN1770510 discloses a kind of preparation method of lithium-ion secondary battery positive plate, comprise that can embed the positive active material that disengages lithium is coated in above the plus plate current-collecting body, baking, calendering, wherein, between baking procedure and calendering step or after the calendering step, with lithium carbonate solution impregnation or spray treatment positive plate surface, and carry out vacuumize.But; in the method; when being impregnated into pole piece in the lithium carbonate solution; positive active material comes off after being soaked into by solvent easily, causes battery capacity to reduce, simultaneously because the flowability of lithium carbonate solution; can't guarantee to form the lithium carbonate protective layer of one deck densification after the positive plate oven dry on the pole piece surface; therefore, still can not effectively stop positive active material and electrolyte to react, use the storge quality and the cycle performance of lithium ion battery of this positive plate still bad.
Summary of the invention
The objective of the invention is to overcome lithium ion battery storge quality and cycle performance defect of bad in the prior art, provide a kind of and have the anode of higher storge quality and cycle performance and use this anodal lithium ion battery.
Another object of the present invention provides the preparation method of anode and uses the preparation method of this anodal lithium ion battery.
The invention provides a kind of anode, this positive pole comprises collector and is coated on the positive electrode coating of the positive electrode on the collector, described positive electrode contains positive active material, conductive agent and adhesive, wherein, described positive pole also comprises second coating, described second coating is coated on the surface of positive electrode coating, and described second coating contains metal oxide, positive active material, conductive agent and adhesive; Described metal oxide is selected from one or more in IIA family metal oxide, group III A metal oxide, IVA family metal oxide, IIB family metal oxide, IIIB family metal oxide and the IVB family metal oxide.
The invention provides a kind of preparation method of anode, this method comprises that the slurry that will contain positive active material, conductive agent, adhesive and solvent is coated on the collector, dry, pressing mold or pressing mold not form the positive electrode coating, it is characterized in that, this method comprises that also the slurry that will contain metal oxide, positive active material, conductive agent, adhesive and solvent is coated on the positive electrode coating, drying, pressing mold or pressing mold not form second coating; Described metal oxide is selected from one or more in IIA family metal oxide, group III A metal oxide, IVA family metal oxide, IIB family metal oxide, IIIB family metal oxide and the IVB family metal oxide.
The invention provides a kind of lithium ion battery, this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, wherein, and described positive pole just very provided by the invention.
The invention provides a kind of preparation method of lithium ion battery, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and barrier film are prepared into a pole piece, and pole piece and the nonaqueous electrolytic solution that obtains is sealed in the battery case, wherein, described positive pole just very provided by the invention.
The present invention is by applying second coating that one deck contains the positive electrode of metal oxide at the positive electrode coating surface; form the metal oxide protective layer of one deck densification on the surface of the outermost active material particle of pole piece; it can suppress the reaction of positive active material and electrolyte; therefore; the battery that uses positive pole of the present invention to prepare has excellent storage performance and cycle performance; especially under high-temperature condition, show out the superiority of battery on storge quality and cycle performance that makes by the present invention more especially.
In addition, only use the metal oxide of minute quantity in the positive electrode of anode provided by the invention, therefore, when achieving the above object, also guaranteed the capacity of battery.Also have, preparation technology of the present invention is simple, and is with low cost.
Embodiment
According to anode provided by the invention, this positive pole comprises collector and is coated on the positive electrode coating of the positive electrode on the collector, described positive electrode contains positive active material, conductive agent and adhesive, wherein, described positive pole also comprises second coating, described second coating is coated on the surface of positive electrode coating, and described second coating contains metal oxide, positive active material, conductive agent and adhesive.
Described metal oxide is selected from one or more in IIA family metal oxide, group III A metal oxide, IVA family metal oxide, IIB family metal oxide, IIIB family metal oxide and the IVB family metal oxide.Under the preferable case, described metal oxide can be ZnO, MgO, CaO, SrO
2, BaO, ZrO
2, TiO
2, Al
2O
3, Ce
2O
3, Y
2O
3Or SnO
2In one or more.Described metal oxide can be commercially available.The consumption of described metal oxide should be enough to form on the surface of the outermost active material particle of pole piece the protective layer of one deck densification, with the reaction of inhibition electrolyte and positive active material, and can too much influence not arranged to battery capacity.In view of the above, be benchmark with the weight of positive active material in second coating, the content of metal oxide described in second coating can be 0.1-5 weight %, is preferably 0.5-3 weight %.
Though arbitrarily the metal oxide of particle diameter can, under the preferable case, the mean particle diameter of metal oxide of the present invention is preferably the 0.01-1 micron.By reducing the particle diameter of metal oxide, can increase its specific area, thereby can make metal oxide under the less situation of consumption, also can form the metal oxide protective layer of one deck densification on the surface of the outermost active material particle of pole piece.
According to positive pole provided by the invention, the positive active material in the described positive electrode coating can be the positive active material of the embedded removal lithium embedded ion of this area routine, one or several in the preferred following material: Li
xM
yMn
2-yO
4, wherein, 0.9≤x≤1.2,0≤y≤1.0, M is a kind of in the elements such as lithium, boron, magnesium, aluminium, iron, cobalt, nickel, copper, gallium, yttrium, fluorine, iodine, sulphur; Li
xNi
yCo
1-yO
2, wherein, 0.9≤x≤1.1,0≤y≤1.0; Li
aNi
xCo
yMn
zO
2, wherein, 0≤a≤1.2, x+y+z=1,0≤x≤0.5,0≤y≤0.5,0≤z≤0.5.Positive active material in second coating can be selected from one or more in the positive active material that described positive electrode coating limited.
According to positive pole provided by the invention, the conductive agent in the described positive electrode coating can be the anodal conductive agent of this area routine, at least a such as in acetylene black, conductive carbon black and the electrically conductive graphite.Conductive agent in second coating can be selected from one or more in the conductive agent that described positive electrode coating limited.Weight with the positive active material in the positive electrode coating is benchmark, and the content of conductive agent described in the positive electrode coating is 1-20 weight %, is preferably 2-15 weight %.Weight with the positive active material in second coating is benchmark, and the content of conductive agent described in second coating is 1-15 weight %, is preferably 2-10 weight %.
According to positive pole provided by the invention, adhesive in the described positive electrode coating can adopt the conventional all types of adhesives that are used to prepare lithium ion cell positive that use in the prior art, for example, can be in polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), butadiene-styrene rubber (SBR) and butadiene-styrene rubber (SBR) latex one or more.Adhesive in second coating can be selected from one or more in the adhesive that described positive electrode coating limited.Weight with the positive active material in the positive electrode coating is benchmark, and the content of adhesive described in the positive electrode coating is 2-10 weight %, is preferably 2-8 weight %.Weight with the positive active material in second coating is benchmark, and bonding content is 2-10 weight % described in second coating, is preferably 2-8 weight %.
According to positive pole provided by the invention, the thickness of described second coating should be moderate.Along with the increase of second coating layer thickness, the shared ratio of metal oxide also increases in the correspondingly whole positive plate, thereby can influence the capacity of battery; On the contrary, along with reducing of second coating layer thickness, the effect that correspondingly suppresses the reaction of positive active material and electrolyte also weakens, and the also corresponding raising of the thin more requirement to slurry of the thickness of coat, can increase the difficulty of practical operation.Therefore, described second coating layer thickness is preferably the 0.01-0.05 millimeter.
According to positive pole provided by the invention, along with the increase of the thickness of described positive electrode coating, the amount of corresponding positive active material also increases, thereby the capacity of battery is increased.But, the described positive electrode coating and second coating layer thickness and should guarantee that electrolyte soaks into pole piece easily, can make lithium ion move at the pole piece internal freedom.Therefore, the positive electrode coating layer thickness is preferably the 0.05-0.24 millimeter.
Further under the preferable case, the described positive electrode coating and second coating and be the 0.06-0.25 millimeter.
According to the present invention, the preparation of described positive electrode coating can be adopted conventional preparation method.For example, described positive active material, conductive agent and adhesive and solvent is even, obtain the positive electrode coating paste, then this positive electrode coating paste is coated on the described collector, drying, pressing mold or pressing mold not form the positive electrode coating.
Described solvent and consumption thereof are conventionally known to one of skill in the art.For example, described solvent can be selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent has viscosity and flowability can make described pastel, can be coated on the described collector to get final product.
In general, be benchmark with the weight of positive active material in the positive electrode coating paste, the content of solvent described in the positive electrode coating paste is 30-80 weight %, is preferably 35-60 weight %; The content of described conductive agent is 1-20 weight %, is preferably 2-15 weight %; The content of described adhesive is 2-10 weight %, is preferably 2-8 weight %.
The method of described drying and pressing mold and condition are conventionally known to one of skill in the art.For example, can place baking oven to toast down and carry out drying in 4-10 hour, carry out pressing mold with tablet press machine at normal temperatures then and get final product at 80-120 ℃.
Described plus plate current-collecting body can for example, can be an aluminium foil for plus plate current-collecting body conventional in the lithium ion battery.
According to the present invention; the preparation of described second coating can be even with described metal oxide, positive active material, conductive agent and adhesive and solvent; obtain second coating paste; then this second coating paste is coated on the described positive electrode coating; dry; pressing mold or pressing mold not form second coating.The positive active material of described second coating, conductive agent, adhesive and solvent can be selected from respectively that the positive electrode coating paste limited positive active material, conductive agent, adhesive and solvent in one or more, described drying can be identical with the preparation method of positive electrode coating with stamping method.
Weight with positive active material in second coating paste is benchmark, and the content of solvent described in second coating paste is 30-80 weight %, is preferably 35-60 weight %; The content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %; The content of described adhesive is 2-10 weight %, is preferably 2-8 weight %.
For metal oxide even compact ground in second coating is distributed, under the preferable case, earlier positive active material and metal oxide are mixed, be dissolved in adhesive in the solvent then after, add the positive active material, the conductive agent that are mixed with metal oxide and prepare second coating paste.The mixing of described metal oxide and positive active material can be carried out in ball mill, and the ball milling time was preferably more than 30 minutes.
According to lithium ion battery provided by the invention, this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, wherein, and described positive pole just very provided by the invention.
The negative pole of battery provided by the invention is conventionally known to one of skill in the art.In general, described negative material contains negative electrode active material, conductive agent and adhesive.
Described negative electrode active material is not particularly limited, can be the negative electrode active material of the embedded removal lithium embedded of this area routine, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, preferred electrographite.
The adhesive of described negative pole comprises one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR).Weight with described negative electrode active material is benchmark, and the content of described adhesive is 0.1-10 weight %, is preferably 0.5-5 weight %.
The conductive agent of described negative pole is not particularly limited, and can be the cathode conductive agent of this area routine, at least a such as in acetylene black, conductive carbon black and the electrically conductive graphite.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
The preparation method of described negative pole can adopt conventional preparation method.For example,, apply and/or be filled on the described collector negative electrode active material, conductive agent and adhesive and solvent, drying, pressing mold or pressing mold not can obtain described negative pole.Wherein, described solvent can be selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described collector to get final product.In general, be benchmark with the weight of negative electrode active material, the content of described solvent is 30-80 weight %, is preferably 35-60 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.Negative current collector can for example, can be a Copper Foil for negative current collector conventional in the lithium ion battery.
Described barrier film is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described pole piece and nonaqueous electrolytic solution are contained in the battery case together.Described barrier film can be selected from various barrier films used in the lithium ion battery, as polyolefin micro porous polyolefin membrane.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9g/Ah, the concentration of electrolyte be generally 0.5-2.9 rub/liter.
According to lithium ion battery provided by the invention, the preparation method of this battery is except described anodal the use the positive pole provided by the invention, and other step is conventionally known to one of skill in the art.In general, the described positive pole for preparing, negative pole and membrane coil around constituting a pole piece, are contained in this pole piece in the battery container, inject electrolyte, then that battery container is airtight, can obtain lithium ion battery provided by the invention.
To the present invention be described in more detail by embodiment below.
Embodiment 1
Present embodiment is used to illustrate anode provided by the invention and uses this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
A: the positive electrode coating paste adopts following method preparation: with 15 gram polyvinylidene fluoride (Atuofeina Corp, 761#PVDF) be dissolved in 225 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and make binder solution, with 15 gram carbon black (TIMICAL company commodity, trade mark is called super-p) be distributed in the above-mentioned binder solution, in gained solution, add 500 gram lithium manganese oxygen then, fully mix and make positive electrode coating paste X1.
B: second coating paste adopts following method preparation: with mean particle diameter D
50Be 8 microns lithium manganese oxygen 500 grams, mean particle diameter D
50Be 0.5 micron Y
2O
35 grams join (Y in the ball mill together
2O
3Weight be lithium manganese oxygen 1%), mix incorporation time 1 hour, the Y that obtains mixing then with the speed of 500rpm
2O
3Mixture with active material.
Prepare second coating paste according to the described method of step a, different is, with the above-mentioned Y that evenly is mixed with
2O
3Lithium manganese oxo for the positive electrode active material lithium manganese oxygen among the step a, make the second coating paste X2.
On aluminium foil, once be coated with positive electrode coating paste X1 in the slurry mode, the positive electrode coating layer thickness is controlled at 0.10 millimeter, toasts 5 hours down at 120 ℃, takes out.On the positive electrode coating, carry out the secondary slurry with the second coating paste X2 then, second coating layer thickness is controlled at 0.01 millimeter, baked 5 hours at 120 ℃ of following sound of a roaring fire, take out, under the pressure of 1.6 MPas, after the roll-in, on cutting machine, cut and make the anode pole piece that is of a size of 550 millimeters (length) * 43.8 millimeter (wide) then.In positive active material total on the anode pole piece (comprising the positive electrode coating and second coating), this anode pole piece contains 6.2 gram positive active materials.
(2) preparation of negative pole
4 gram binding agent Kynoar (PVDF) are dissolved in the N-methyl pyrrolidones of 50 grams binder solution, with the graphite of 100 grams (the soddif commodity, DAG22) and 4 gram conductive agent carbon black dispersion in above-mentioned binder solution, obtain cathode size.Above-mentioned cathode size is coated to equably the two sides of the Copper Foil that serves as collector, thickness is 10 microns, toasts 5 hours down at 120 ℃ then, takes out, under the pressure of 1.6 MPas, after the roll-in, on cutting machine, cut and make the cathode pole piece that is of a size of 515 millimeters (length) * 44.5 millimeter (wide).This cathode pole piece contains 3.0 gram negative electrode active materials.
(3) assembling of battery
The polypropylene screen of above-mentioned positive and negative plate and 20 micron thickness is wound into the pole piece of a rectangular lithium ion battery, in the battery case of packing into and weld, subsequently with LiPF
6Be dissolved in by the concentration of 1 mol in the mixed solvent of EC/DMC (vinyl carbonate/diethyl carbonate)=1: 1 and form nonaqueous electrolytic solution, this electrolyte is injected battery case with the amount of 3.8g/Ah, sealing, make 453450A type (thick 4.5mm, wide 34mm, high 50mm) lithium rechargeable battery A1.
Comparative Examples 1
According to the method preparation example ion battery of embodiment 1, different is that the thickness of the positive electrode coating of anode is 0.11 millimeter, does not have second coating on this positive pole, makes lithium ion battery B1.
Comparative Examples 2
According to the method preparation example ion battery of embodiment 1, different is, the thickness of the secondary coating of anode is 0.11 millimeter, and no positive electrode coating makes lithium ion battery B2 on this positive pole.
Comparative Examples 3
Method according to embodiment 1 prepares lithium ion battery, different is that the thickness of the positive electrode coating of anode is 0.11 millimeter, and this anode pole piece is after drying, dipping took out after 20 minutes in the lithium carbonate aqueous solution of 1 liter 0.01 weight % again, carried out obtaining after the vacuumize.Make lithium ion battery B3.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery, different is, the positive active material in the anode is a lithium cobalt oxygen, and the thickness of the positive electrode coating of anode is 0.24 millimeter, the thickness of second coating is 0.01 millimeter, and used metal oxide is SnO in second coating
2, mean particle diameter is 0.1 micron, metal oxide SnO among the second coating paste X2
2Consumption be 0.5 the gram (SnO
2Weight be among the second coating paste X2 lithium cobalt oxygen weight 0.1%), make lithium ion battery A2.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery, and different is, the thickness of the positive electrode coating of anode is 0.15 millimeter, and the thickness of second coating is 0.05 millimeter, and used metal oxide is ZrO in second coating
2, mean particle diameter is 0.3 micron, metal oxide ZrO among the second coating paste X2
2Consumption be 10 the gram (ZrO
2Weight be among the second coating paste X2 lithium manganese oxygen weight 2%), make lithium ion battery A3.
Embodiment 4
Method according to embodiment 1 prepares lithium ion battery, different is, the thickness of the positive electrode coating of anode is 0.06 millimeter, the thickness of second coating is 0.02 millimeter, used metal oxide is BaO, mean particle diameter is 0.8 micron, among the second coating paste X2 consumption of metal oxide BaO be 15 the gram (weight of BaO be among the second coating paste X2 lithium manganese oxygen weight 3%), make lithium ion battery A4.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery, and different is, the thickness of second coating of anode is 0.03 millimeter, and used metal oxide is Al in second coating
2O
3, mean particle diameter is 1 micron, metal oxide Al among the second coating paste X2
2O
3Consumption be 20 the gram (Al
2O
3Weight be among the second coating paste X2 lithium manganese oxygen weight 4%), make lithium ion battery A5.
Embodiment 6
Method according to embodiment 1 prepares lithium ion battery, different is, the thickness of second coating of anode is 0.04 millimeter, used metal oxide is ZnO in second coating, mean particle diameter is 0.01 micron, among the second coating paste X2 consumption of metal oxide ZnO be 25 the gram (weight of ZnO be among the second coating paste X2 lithium manganese oxygen weight 5%), make lithium ion battery A6.
Embodiment 7
Method according to embodiment 1 prepares lithium ion battery, and different is, among the positive electrode slurry X1, the conductive agent of adding is 50 grams, and adhesive is 40 grams, and solvent is 300 grams.Make lithium ion battery A7.
Embodiment 8
The performance of the battery A1 that present embodiment is used to illustrate that the embodiment of the invention 1 makes.
(1) cycle performance test
Constant current with 800mA carries out constant current charge to above-mentioned battery, and charging rises to 4.2V at voltage and carries out constant voltage charge later on, by electric current 25mA by voltage 4.2V; Shelved 10 minutes, and to 3.0V, measured the initial discharge capacity that obtains battery with the current discharge of 800mA.After shelving 10 minutes, repeat above step, make continuous charge-discharge test, obtain the discharge battery capacity after battery circulates for 400 times, calculate the discharge capacitance of 400 circulation back batteries according to following formula.The result is as shown in table 1.
Discharge capacitance=400 time circulation back discharge capacity/initial discharge capacity * 100%
(2) high-temperature storage performance test
Constant current with 800mA carries out constant current charge to above-mentioned battery, and charging rises to 4.2V at voltage and carries out constant voltage charge later on, by electric current 25mA by voltage 4.2V; Shelved 10 minutes, and to 3.0V, obtained battery capacity and accurate recording cell thickness with the current discharge of 800mA.Once more with battery charge to 4.2V, in 85 ℃ thermostat, placed 48 hours.After the preservation, again with the current discharge of 800mA to 3.0V, measure battery capacity and cell thickness then.Counting cell capacity sustainment rate and varied in thickness.The result is as shown in table 1.
Battery capacity * 100% before battery capacity sustainment rate=storage back battery capacity/storage
Comparative Examples 4-6
The performance of the battery B1-B3 that these embodiment are used to illustrate that Comparative Examples 1-3 makes.
Method according to embodiment 8 is carried out performance test to battery B1-B3.The result is as shown in table 1.
Embodiment 9-14
The performance of the battery A2-A7 that these embodiment are used to illustrate that embodiment of the invention 2-7 makes.
Method according to embodiment 8 is carried out performance test to battery A2-A7.The result is as shown in table 1.
Table 1
From the result shown in the table 1 as can be seen, all more than 810 MAHs, 400 circulation back capability retentions are all more than 85% in the cycle performance test for the initial discharge capacity of the battery A1-A7 that embodiment 1-7 prepares; In addition, after the test of high-temperature storage performance, the capacity sustainment rate all is higher than 80%, and varied in thickness is all below 0.2 millimeter.Illustrate that the battery that positive pole of the present invention prepares has excellent storage performance and cycle performance.
Do not contain second coating in the positive pole of the battery B1 that Comparative Examples 1 prepares, the battery A1-A7 that the initial discharge capacity of this battery and embodiment 1-7 prepare is close; But 400 circulation back capability retention less thaies 80%, the capacity sustainment rate less than 70% in the test of high-temperature storage performance, and varied in thickness is bigger.
Do not contain the positive electrode coating in the positive pole of the battery B2 that Comparative Examples 2 prepares, the battery A1-A7 that this battery all prepares with embodiment 1-7 on cycle performance and high-temperature storage performance is close, and still, its battery capacity only is 763 MAHs.
Comparative Examples 3 is the battery B3 that prepare according to the CN1770510 disclosed method, and it is by forming the reaction that one deck lithium carbonate protective layer suppresses positive active material and electrolyte on the anode pole piece surface.But, because the flowability of lithium carbonate solution can't guarantee after the anode pole piece oven dry that the battery A1-A7 that the initial discharge capacity of this battery and embodiment 1-7 prepare is close at the lithium carbonate protective layer of pole piece surface formation one deck densification; But 400 times circulation back capability retention only is 81%, the capacity sustainment rate less than 70% in the test of high-temperature storage performance, and varied in thickness is bigger.
In sum, the battery according to the preparation method of anode of the present invention and battery obtains has good cycle performance and storge quality.
Claims (20)
1. anode, this positive pole comprises collector and is coated on positive electrode coating on the collector, described positive electrode contains positive active material, conductive agent and adhesive, it is characterized in that, described positive pole also comprises second coating, described second coating is coated on the surface of positive electrode coating, and described second coating contains metal oxide, positive active material, conductive agent and adhesive; Described metal oxide is selected from one or more in IIA family metal oxide, group III A metal oxide, IVA family metal oxide, IIB family metal oxide, IIIB family metal oxide and the IVB family metal oxide; Described positive electrode coating is identical with positive active material in described second coating.
2. positive pole according to claim 1, wherein, the mean particle diameter of described metal oxide is the 0.01-1 micron.
3. positive pole according to claim 1, wherein, weight with the positive active material in second coating is benchmark, and the content of metal oxide is that the content of 0.1-5 weight %, conductive agent is that the content of 1-15 weight %, adhesive is 2-10 weight % in second coating.
4. positive pole according to claim 3, wherein, weight with the positive active material in second coating is benchmark, and the content of metal oxide is that the content of 0.5-3 weight %, conductive agent is that the content of 2-10 weight %, adhesive is 2-8 weight % in second coating.
5. according to any described positive pole among the claim 1-4, wherein, described metal oxide is ZnO, MgO, CaO, SrO
2, BaO, ZrO
2, TiO
2, Al
2O
3, Ce
2O
3, Y
2O
3Or SnO
2In one or more.
6. positive pole according to claim 1, wherein, the thickness of described second coating is the 0.01-0.05 millimeter; The thickness of described positive electrode coating is the 0.05-0.24 millimeter.
7. positive pole according to claim 6, wherein, the thickness of the described positive electrode coating and second coating and be the 0.06-0.25 millimeter.
8. positive pole according to claim 1 wherein, is a benchmark with the positive active material in the positive electrode coating, and the content of conductive agent is 1-20 weight % in the positive electrode coating, and binder content is 2-10 weight %.
9. positive pole according to claim 8 wherein, is a benchmark with the positive active material in the positive electrode coating, and the content of conductive agent is 2-15 weight % in the positive electrode coating, and binder content is 2-8 weight %.
10. the preparation method of the described positive pole of claim 1, this method comprises that the positive electrode coating paste that will contain positive active material, conductive agent, adhesive and solvent is coated on the collector, dry, pressing mold or pressing mold not form the positive electrode coating, it is characterized in that, this method comprises that also second coating paste that will contain metal oxide, positive active material, conductive agent, adhesive and solvent is coated on the positive electrode coating, drying, pressing mold or pressing mold not form second coating; Described metal oxide is selected from one or more in IIA family metal oxide, group III A metal oxide, IVA family metal oxide, IIB family metal oxide, IIIB family metal oxide and the IVB family metal oxide; Described positive electrode coating is identical with positive active material in described second coating.
11. method according to claim 10, wherein, the mean particle diameter of described metal oxide is the 0.01-1 micron.
12. method according to claim 10, wherein, weight with the positive active material in second coating paste is benchmark, the content of metal oxide is that the content of 0.1-5 weight %, conductive agent is that the content of 1-15 weight %, adhesive is 2-10 weight % in second coating paste, and the content of solvent is 30-80 weight %.
13. method according to claim 12, wherein, weight with the positive active material in second coating paste is benchmark, the content of metal oxide is that the content of 0.5-3 weight %, conductive agent is that the content of 2-10 weight %, adhesive is 2-8 weight % in second coating paste, and the content of solvent is 35-60 weight %.
14. according to any described method among the claim 10-13, wherein, described metal oxide is ZnO, MgO, CaO, SrO
2, BaO, ZrO
2, TiO
2, Al
2O
3, Ce
2O
3, Y
2O
3Or SnO
2In one or more.
15. method according to claim 10, wherein, the thickness of described second coating is the 0.01-0.05 millimeter; The thickness of described positive electrode coating is the 0.05-0.24 millimeter.
16. method according to claim 15, wherein, the thickness of the described positive electrode coating and second coating and be the 0.06-0.25 millimeter.
17. method according to claim 10, wherein, be benchmark with the positive active material in the positive electrode coating paste, the content of conductive agent is 1-20 weight % in the positive electrode coating paste, binder content is 2-10 weight %, and the content of solvent is 30-80 weight %.
18. method according to claim 17, wherein, be benchmark with the positive active material in the positive electrode coating paste, the content of conductive agent is 1-20 weight % in the positive electrode coating paste, binder content is 2-10 weight %, and the content of solvent is 35-60 weight %.
19. lithium ion battery, this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, it is characterized in that any described positive pole among the described just very claim 1-9.
20. the preparation method of the described battery of claim 19, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and barrier film are prepared into a pole piece, the pole piece and the nonaqueous electrolytic solution that obtain are sealed in the battery case, it is characterized in that any described positive pole among the described just very claim 1-9.
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| CN101242209B (en) * | 2007-02-09 | 2011-09-21 | 中国移动通信集团公司 | Uplink macro sub-set processing method in mobile communication system |
| KR20120089845A (en) * | 2009-08-27 | 2012-08-14 | 엔비아 시스템즈 인코포레이티드 | Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling |
| CN102412387A (en) * | 2010-09-26 | 2012-04-11 | 比亚迪股份有限公司 | Positive pole of lithium ion battery, and manufacturing method for positive pole, and lithium ion battery |
| CN103560250A (en) * | 2013-11-07 | 2014-02-05 | 天津市捷威动力工业有限公司 | Lithium ion battery adopting lithium-rich manganese-based material as positive electrode and preparation method of lithium ion battery |
| CN108539198B (en) * | 2017-03-03 | 2023-02-28 | 易案爱富科技有限公司 | Solvent for coating positive electrode active material for secondary battery, positive electrode active material slurry containing same, and secondary battery manufactured therefrom |
| CN109768220A (en) * | 2018-12-28 | 2019-05-17 | 东莞凯德新能源有限公司 | A method of reducing lithium ion battery self discharge |
| CN110581255B (en) * | 2019-10-18 | 2020-11-24 | 宇恒电池有限公司 | Lithium ion battery anode and method for preparing lithium ion battery anode |
| CN115411220A (en) * | 2022-09-13 | 2022-11-29 | 珠海冠宇电池股份有限公司 | Positive plate, battery core and battery |
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| CN1658413A (en) * | 2004-02-17 | 2005-08-24 | 比亚迪股份有限公司 | Lithium cell plus plate and its preparation method and lithium ion secondary battery |
| CN1770510A (en) * | 2004-11-06 | 2006-05-10 | 比亚迪股份有限公司 | Method for preparing lithium secondary battery anode tab and lithium ion secondary battery |
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| CN1658413A (en) * | 2004-02-17 | 2005-08-24 | 比亚迪股份有限公司 | Lithium cell plus plate and its preparation method and lithium ion secondary battery |
| CN1770510A (en) * | 2004-11-06 | 2006-05-10 | 比亚迪股份有限公司 | Method for preparing lithium secondary battery anode tab and lithium ion secondary battery |
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