CN207409587U - A kind of lithium battery anode - Google Patents
A kind of lithium battery anode Download PDFInfo
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- CN207409587U CN207409587U CN201721293447.8U CN201721293447U CN207409587U CN 207409587 U CN207409587 U CN 207409587U CN 201721293447 U CN201721293447 U CN 201721293447U CN 207409587 U CN207409587 U CN 207409587U
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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 utility model belongs to a kind of lithium battery anode, belongs to technical field of lithium batteries, overcome the deficiencies in the prior art, it is therefore an objective to provide a kind of high-performance lithium anode, the scheme of use：Including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, it is characterised in that：Composite bed of the plus plate current-collecting body at least one side coated with bonding agent, positive pole powder and conductive black composition, the plus plate current-collecting body is a kind of micropore aluminium foil, and the micropore aluminium foil is dispersed with multiple through holes and/or multiple blind holes；The composite bed being made of in the through hole and/or blind hole bonding agent, positive pole powder and conductive black, the utility model can be used in lithium battery.
Description
Technical field
The utility model belongs to a kind of lithium battery anode, belongs to technical field of lithium batteries.
Background technology
New material and clean energy resource are all the prior development directions of State-level, and lithium ion battery is in current energy storage technology
Most widely used energy storage battery core, it is the target that the whole world is pursued to improve battery core energy storage density, and battery core energy density carries
Height depends on the progress of its positive and negative electrode material, but is also bonded with the positive and negative anodes collector of lithium ion battery, positive and negative anodes
The progress of the materials such as agent, electrolyte and membrane is related.
The positive mix that the collector that the anode of lithium ion battery uses is generally aluminium foil and is coated on（Ferric phosphate
Lithium, cobalt acid lithium or ternary material）It is formed.Traditional current collector material generally selects the smooth aluminium foil in surface, pure using 99.7%
The aluminium foil of degree directly applies and is covered with active material, but the combination between the smooth aluminium foil and active material in surface more relaxes, to original
Material and auxiliary material quality and technological requirement are high, and active material easily occurs in processing and charge and discharge process and comes off or lose powder phenomenon,
Cycle charge discharge electrical efficiency and battery life are reduced, improves the contact resistance between component, positive plate electric conductivity is caused to decline,
So as to affect the comprehensive performance of battery.The serious comprehensive performance for affecting lithium ion.People are generally using roughening aluminium at present
The method on paper tinsel surface increases the cohesion between aluminium foil and positive mix, but the technique can not reach desired effect.Just
Pole powder and aluminium foil separation problem can all occur when winding prismatic battery and during cycle charge-discharge, and then product is caused to close
Lattice rate first mate reduces, service life first mate shortens and battery capacity attenuation is apparent, and the battery for using ternary material is influenced the most
Seriously.
In order to improve positive pole aluminium foil collector, the bond state between anode sizing agent, some Japanese and Taiwan enterprises
Micropore copper foil and micropore aluminium foil are developed, is all prepared for nine through holes on both positive and negative anodes collector foils are every square centimeter,
The diameter of each through hole is about 1mm.But the aluminium foil and copper foil prepared by them must use special battery automatic assembly line,
Reason is on original battery automatic assembly line, using such through-hole diameter in the copper foil or aluminium foil of 1mm, it may appear that the back of the body
Slurry phenomenon is oozed in face, influences the coating of another side.
Han Wei et al. utilizes acid, alkali electroless reagent in patent CN 103618090A and CN 103617894A, right
Aluminium foil carries out soda acid etching processing.Obtained alumina foil contact resistance reduces unobvious, and is reduced during corrosion removal
The mechanical strength of aluminium foil.The method of other countries' pore-forming on aluminium foil, employs rolling or laser ablation, and the utility model
Aluminium foil pore-forming using salt compounds etch, technology path is entirely different, and obtained micropore aluminium foil also has spy
Different structure and performance.
Utility model content
The utility model overcome the deficiencies in the prior art, it is therefore an objective to which a kind of high-performance lithium anode is provided.
In order to solve the above technical problems, technical solution is used by the utility model：A kind of lithium battery anode, including：
Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, the plus plate current-collecting body at least one side is coated with bonding agent, anode
The composite bed of powder and conductive black composition,
The plus plate current-collecting body is a kind of micropore aluminium foil, and the micropore aluminium foil is dispersed with multiple through holes and/or multiple
Blind hole.
Further, the upper and lower surface of the micropore aluminium foil is dispersed with multiple indentations.
Further, the plus plate current-collecting body dual coating is answered by what bonding agent, positive pole powder and conductive black formed
Close layer.
Further, it is made of in the through hole and/or blind hole bonding agent, positive pole powder and conductive black compound
Layer.
Further, the through hole and blind hole are irregular shape, and are irregular with micropore aluminium foil surface junction
Arc transition.
Further, the positive pole powder or it is ternary material or is LiFePO4 or is cobalt acid lithium.
The utility model has the advantages that compared with prior art：
1st, a kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, it is characterised in that：
Composite bed of the pole collector at least one side coated with bonding agent, positive pole powder and conductive black composition, the anode
Powder is ternary material or is LiFePO4 or is cobalt acid lithium；The plus plate current-collecting body is a kind of micropore aluminium foil, described
Plus plate current-collecting body be distributed with for a kind of micropore aluminium foil, on the micropore aluminium foil is every square centimeter 1000-1500 it is a diameter of
10-50 μm of through hole and/or 1000-3000 a diameter of 10-50 μm of blind holes；It is coated in the through hole and/or blind hole
The mixture of positive pole powder and bonding agent.So that two surfaces of metal foil are not both completely through or without completely isolated, energy
Effectively by the ion of smaller less than 10-50 μm of diameter and particle, as lithium ion by, and prevent major diameter from
Son or particle by, while do not influence the performance of material, such as：Average resistivity increases by 1-3%, and average tensile strength is promoted
0-2%, it is averagely broken breaking elongation and promotes 0-21%.Plus plate current-collecting body can have positive pole powder and bonding agent with dual coating
Mixture.
2nd, it is further, indentation is dispersed in the upper and lower surface of the micropore aluminium foil, indentation is 1-3 μm deep, wide 1-5 μ
M, the through hole and blind hole are irregular shape and irregular distribution, and are irregular circular arc with micropore aluminium foil surface junction
Transition.The through hole and blind hole are irregular shape, and are irregular arc transition with aluminium foil surface junction, aperture size
Change within the specific limits, the diameter of each hole is also varied from different directions.Can be promoted micropore aluminium foil two sides into
During row coating, the adhesive force of coating, through hole and blind hole and material body arc transition are promoted, reduces stress concentration, enhances mechanics
Performance will not weaken electric property.
Micropore aluminium foil as lithium battery anode collector, have on its is every square centimeter 1000-1500 diameters 10-
The blind hole of 50 μm of through hole and 1000-3000 diameters at 10-50 μm makes two surfaces inside and outside micropore aluminium foil both no complete
, can be by lithium particle through also without completely isolated, and other particles or particle are prevented by the way that lithium ion passes through plus plate current-collecting body
Afterwards, can move about in entire lithium battery, improve lithium ion activity, improve battery capacity, coated in positive electrode above with
Aluminium foil is integral, and adhesive force significantly improves, and Li dendrite will not be grown at through hole and blind hole.
3rd, a kind of method for preparing lithium battery anode, the step including preparing plus plate current-collecting body using the method for chemical corrosion
Suddenly.Other are same or like with the existing method for preparing lithium battery anode, a kind of method for preparing positive current collector material, use
The method of chemical liquids corrosive aluminum foil may be employed conventional acid solution corrosion, can also use conventional alkali soluble corrosion, can be with
Using pure salting liquid, reduce environmental pollution.
The utility model also can be used using being different from general acid ＆ alkali liquid corrosive liquid in the utility model caustic solution
Chloride salt compound is as corrosive liquid, the extent of reaction milder during corrosion, when aluminium foil is put into treatment fluid, chlorine from
Under the protection of son, copper ion or iron ion react with aluminium surface, make the structure of aluminium surface formation micropore, the calcium in treatment fluid
Ion, sodium ion and barium ions, which enter in perforated membrane, to be fixed in the follow-up process, and improvement is played to aluminium surface performance
Effect.
The size for the micropore aluminium foil hole that a kind of method for preparing lithium battery anode of the utility model prepares is much smaller than
The aperture of micropore aluminium foil prepared by the prior art, while the too small caused positive electrode of hole is in turn avoided inside and outside aluminium foil
The problem of table can not penetrate, the micropore aluminium foil of the utility model make micropore aluminium foil surface due to the hole and indentation of particular size
Smoothness higher is irregular arc transition without overlap, burr, and hole and aluminium foil surface junction, straight there is no 90 °
Angle can effectively prevent the appearance of Li dendrite in charge and discharge process, extend the service life of battery；In addition, micro-pore shape also has
Institute is different, and the hole on micropore aluminium foil obtained by chemical corrosion method is in irregular shape, and aperture size is in 10-50 μ ms
Variation, the diameter of each hole are also varied from different directions, and the hole of this irregular shape is more advantageous to improving aluminium
Cohesive force between paper tinsel and anode sizing agent.And existing production technology is varied without, easy to spread, it is not only suitable for single side coating
Suitable for dual coating.
Compared with primary battery aluminium foil, the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；Micropore aluminium foil
Resistivity is increased only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses ternary material,
Since micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, the property such as capacity and charge-discharge characteristics of battery can be made
The uniformity of energy is substantially improved, and battery production yield rate improves 15-20%.
Description of the drawings
Fig. 1 is a kind of structure diagram of lithium battery anode of the utility model.
Fig. 2 is the micro image of plus plate current-collecting body in a kind of lithium battery anode of the utility model.
Fig. 3 is the stress strain curve figure of plus plate current-collecting body in a kind of lithium battery anode of the utility model.
Specific embodiment
Embodiment 1
A kind of lithium battery anode, including：Plus plate current-collecting body 1, bonding agent, positive pole powder, conductive black, the pole afflux
Composite bed 2 of the body at least one side coated with bonding agent, positive pole powder and conductive black composition, the positive pole powder or for ternary
Material is LiFePO4 or is cobalt acid lithium；There are bonding agent, positive pole powder and conductive charcoal in the through hole 3 and/or blind hole 4
The composite bed 2 of black composition, the composite bed 2 are identical with the composite bed of the prior art.
The plus plate current-collecting body is a kind of micropore aluminium foil, it is distributed with 1000 on the micropore aluminium foil is every square centimeter-
The blind hole 4 of 1500 a diameter of 10-50 μm of 3 and/or 1000-3000 a diameter of 10-50 μm of through hole；The through hole 3
And/or the composite bed 2 of bonding agent, positive pole powder and conductive black composition is coated in blind hole 4, above and below the micropore aluminium foil
Surface is dispersed with multiple indentations, and the indentation is 1-3 μm deep, 1-5 μm wide, 100-1000 μm long, the through hole and blind
Hole is irregular shape, and is irregular arc transition with micropore aluminium foil surface junction.
It follows the steps below：
The step of a kind of method for preparing lithium battery anode, wherein micropore aluminium foil are made of chemical liquids caustic solution is such as
Under, other steps are same as the prior art or similar, here, not repeating.
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 5g/L
The Na of NaOH, 70g/L2CO3, 40g/L Na3PO4, by the aluminium foil after rolling by the first cleaning solution, in the first cleaning solution
The time of holding is 6s.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 0.5mol/L,
The BaCl of 0.1mol/L2, 0.1mol/L CaCl2, 0.1mol/L NH4The CuCl of Cl, 0.1mol/L2, 0.1mol/L
FeCl3, residence time of the aluminium foil in the corrosive agent in 20s, in this stage, it is ensured that aluminium foil upper and lower surface is immersed in corrosion simultaneously
In liquid, and the type of flow for cycling corrosive liquid is flowed in aluminium foil upper and lower surface, makes upper and lower surface corrosion uniform to reach.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is to take 0.4-0.8g/LNa2SO4、0.5—
1g/LCaSO4, 0.1-0.3g/L citric acids, aluminium foil upper and lower surface using nozzle spray the second cleaning solution cleaned.
4）Brightization processing：The composition of brightening liquid is the CrO of 2g/L3, 1g/L Na2Cr2O7•2H2O, the NaF of 0.1g/L,
Surface brightening processing is carried out to the aluminium foil after cleaning.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 200 DEG C.
7）Finished product is wound.
Fig. 1 be a kind of structure diagram of lithium battery anode of the utility model, coated on both sides have bonding agent, positive pole powder and
The composite bed 2 of conductive black composition, bonding agent, positive pole powder and conductive black can into plus plate current-collecting body 1 through hole 3 or/
In blind hole 4.
Fig. 2 is the micro image of plus plate current-collecting body in a kind of lithium battery anode of the utility model, the material of plus plate current-collecting body
For battery micropore aluminium foil, as can be seen that two surfaces are not both completely through or without completely inside and outside micropore aluminium foil from Fig. 1
Isolation, integral with aluminium foil coated in positive electrode above, adhesive force significantly improves.
Fig. 3 is the stress strain curve figure of plus plate current-collecting body in a kind of lithium battery anode of the utility model, the material of plus plate current-collecting body
Expect for battery micropore aluminium foil, curve 1 is the stress strain curve of primary battery aluminium foil in figure, and curve 2 is bent for the stretching of battery micropore aluminium foil
Line, the battery micropore aluminium foil after chemical attack, tensile property compared with primary battery aluminium foil there is no reducing, it is close instead or have
It is improved.
The present embodiment is assembled into lithium ion battery：8.5g LiFePO4s, 1.0g acetylene blacks and 0.5g PVDF are weighed,
And 20g NMP are added in, it is sufficiently stirred the slurry for making uniformly mixed.Then scratched in through the utility model embodiment
In the 1 micropore aluminum foil current collector handled well, 80 DEG C of dryings are to constant weight under the vacuum of 0.01MPa, and in 10-15MPa pressure
Lower roll is pressed into iron phosphate lithium electrode, and is cut into anode disk.Equally, 4.25g graphite, 0.5g acetylene blacks and 0.25g are weighed
Butadiene-styrene rubber binding agent, and 10g NMP are added in, the slurry for making uniformly mixed is sufficiently stirred, is then scratched in warp
On the common copper foil that ethyl alcohol cleaned, negative plate is pressed into.By positive plate, celgard2400 polypropylene porous films membrane, bear
Lamination assembling is into battery core in sequence for pole piece, then with battery housing seal battery core, toward battery case in inject 1mol/L's
LiBF4/ diethyl carbonate electrolyte, seals liquid injection port after being full of, obtains lithium ion battery.
At a temperature of 60 DEG C, using charge-discharge test instrument to being assembled in the present embodiment in the voltage range of 2.5-4.2V
Lithium ion battery carry out 1C charge-discharge tests, the specific discharge capacity of the 3rd time is 179mAh/g, carries out 300 charge and discharge and follows
After ring, capacity retention ratio 95.6%.
To further illustrate a kind of advantageous effect of lithium battery anode of the utility model, spy sets following comparative example：
8.5g LiFePO4s, 1.0g acetylene blacks and 0.5g PVDF are weighed, and adds in 20g NMP, is sufficiently stirred and is allowed into
For uniformly mixed slurry.Then scratched in the normal aluminium foil cleaned through ethyl alcohol, 80 under the vacuum of 0.01MPa
It is DEG C dry to be pressed into iron phosphate lithium electrode to constant weight, and in 10-15MPa pressure lower rolls, and it is cut into anode disk.Equally, claim
4.25g graphite, 0.5g acetylene blacks and 0.25g butadiene-styrene rubber binding agents are taken, and adds in 10g NMP, is sufficiently stirred and makes
Then uniformly mixed slurry is scratched on the common copper foil cleaned through ethyl alcohol, is pressed into negative plate.By positive plate,
Lamination assembling is electric into battery core, then with battery housing seal in sequence for celgard2400 polypropylene porous films membrane, negative plate
Core, toward battery case in inject 1mol/L LiBF4/ diethyl carbonate electrolyte, seal liquid injection port after filling, obtain lithium from
Sub- battery.
After testing, after 300 charge and discharge cycles, capacity retention ratio is lithium ion battery obtained by the comparative example
82.5%.It can be seen that micropore aluminum foil current collector made from the present embodiment, since the hole of this irregular shape thereon more has
Beneficial to the cohesive force improved between aluminium foil and anode sizing agent, coming off for positive electrode can be avoided, so as to improve lithium ion battery
Cyclical stability and the service life.
A kind of micropore aluminium foil of lithium battery anode of the utility model due to the hole and indentation of specific 10-50 μm of sizes,
Can be by lithium ion, and other adiaphorous particles or ion cannot be by adding lithium battery capacity, making micropore aluminium foil surface
Smoothness higher is irregular arc transition without overlap, burr, and hole and aluminium foil surface junction, straight there is no 90 °
Angle can effectively prevent the appearance of Li dendrite in charge and discharge process, extend the service life of battery；In addition, micro-pore shape also has
Institute is different, and the hole on micropore aluminium foil obtained by chemical corrosion method changes within the specific limits in irregular shape, aperture size,
The diameter of each hole is also varied from different directions, the hole of this irregular shape be more advantageous to improving aluminium foil with just
Cohesive force between the slurry of pole.And existing production technology is varied without, easy to spread, it is not only suitable for single side coating and is also applied for
Dual coating.
Compared with primary battery aluminium foil, the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；Micropore aluminium foil
Resistivity is increased only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses ternary material,
Since micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, the property such as capacity and charge-discharge characteristics of battery can be made
The uniformity of energy is substantially improved, and battery production yield rate improves 15-20%.
Embodiment 2
A kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, the pole afflux
Body at least one side is coated with the composite bed of bonding agent, positive pole powder and conductive black, the positive pole powder or for ternary material,
Or it is LiFePO4 or is cobalt acid lithium；There is answering for bonding agent, positive pole powder and conductive black in the through hole and/or blind hole
Close layer.
The plus plate current-collecting body be a kind of micropore aluminium foil, material be battery aluminium foil, every square of the battery micropore aluminium foil
There are 1000-1500 diameters in the through hole of 10-15 μm of size unevenness and 1000-3000 diameters at 10-50 μm on centimetre
The blind hole of size unevenness, each through hole and blind hole are irregular shape, and each hole is irregular roundness with aluminium foil surface junction
Arc transition, and the diameter on different directions is different；The upper and lower surface of aluminium foil is dispersed with the deep mixed indentation of multiple length simultaneously,
Indentation is 1-3 μm deep, 1-5 μm wide, and long 100-1000 μm are differed, and the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μ also can be selected
M, 16 μm, 20 μm etc..
Micropore aluminium foil is made of chemical liquids caustic solution, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 30g/L
The Na of NaOH, 70g/L2CO3, 40g/L Na3PO4, by the aluminium foil after rolling by the first cleaning solution, in the first cleaning solution
The time 10s of holding.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 1.5mol/L,
The BaCl of 0.3mol/L2, 0.5mol/L CaCl2, 0.5mol/L NH4The CuCl of Cl, 0.8mol/L2, 1mol/L
FeCl3, residence time of the aluminium foil in the corrosive agent in 120s, in this stage, it is ensured that aluminium foil upper and lower surface is immersed in corruption simultaneously
It loses in liquid, and the type of flow for cycling corrosive liquid is flowed in aluminium foil upper and lower surface, makes upper and lower surface corrosion equal to reach
It is even.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is to take 0.4-0.8g/LNa2SO4、0.5—
1g/LCaSO4, 0.1-0.3g/L citric acids, aluminium foil upper and lower surface using nozzle spray the second cleaning solution cleaned.
4）Brightization processing：The composition of brightening liquid is 5g/L CrO3、7g/L Na2Cr2O7•2H2O, 1.5g/L NaF, to clear
Aluminium foil after washing carries out surface brightening processing.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 300 DEG C.
7）Finished product is wound.
Embodiment 3
A kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, the pole afflux
Body at least one side is coated with the composite bed of bonding agent, positive pole powder and conductive black, the positive pole powder or for ternary material,
Or it is LiFePO4 or is cobalt acid lithium；There is answering for bonding agent, positive pole powder and conductive black in the through hole and/or blind hole
Close layer.
The plus plate current-collecting body is a kind of micropore aluminium foil, and material is battery micropore aluminium foil, and battery micropore aluminium foil is often put down
There are 1000-1500 diameters in the through hole of 10-15 μm of size unevenness and 1000-3000 diameters in 10-50 μ on square centimetre
The blind hole of m sizes unevenness, each through hole and blind hole are irregular shape, and each hole is irregular roundness with aluminium foil surface junction
Arc transition, and the diameter on different directions is different；The upper and lower surface of aluminium foil is dispersed with the deep mixed indentation of multiple length simultaneously,
Indentation is 1-3 μm deep, 1-5 μm wide, and long 100-1000 μm are differed, and the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μ also can be selected
M, 16 μm, 20 μm etc..
Battery micropore aluminium foil is made of chemical liquids heat erosion method, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 17g/L
The Na of NaOH, 40g/L2CO3, 25g/L Na3PO4, the temperature of the first cleaning solution is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Paper tinsel is by the first cleaning solution, the time 15s kept in the first cleaning solution.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：1mol/L NaCl、0.2mol/
L BaCl2、0.3mol/L CaCl2、0.3mol/L NH4Cl、0.45mol/LCuCl2、0.55mol/LFeCl3, the temperature of corrosive liquid
Degree is maintained at 45 ± 2 DEG C, residence time of the aluminium foil in the corrosive agent in 70s, in this stage, it is ensured that aluminium foil upper and lower surface is simultaneously
It is immersed in corrosive liquid, and the type of flow for cycling corrosive liquid is flowed in aluminium foil upper and lower surface, makes upper following table to reach
Face corrosion is uniform.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is to take 0.4-0.8g/LNa2SO4、0.5—
1g/LCaSO4, 0.1-0.3g/L citric acids, the temperature of the second cleaning solution is maintained at 45 ± 2 DEG C.Make in aluminium foil upper and lower surface
The second cleaning solution is sprayed with nozzle to be cleaned.
4）Brightization processing：The composition of brightening liquid is 3.5g/L CrO3、4g/L Na2Cr2O7•2H2O, 0.8g/L NaF are right
Aluminium foil after cleaning carries out surface brightening processing, and the temperature of brightening liquid is maintained at 45 ± 2 DEG C.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution, the
The temperature of two cleaning solutions is maintained at 45 ± 2 DEG C,.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 60 DEG C.
7）Finished product is wound.
Embodiment 4
A kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, the pole afflux
Body at least one side is coated with the composite bed of bonding agent, positive pole powder and conductive black, the positive pole powder or for ternary material,
Or it is LiFePO4 or is cobalt acid lithium；There is answering for bonding agent, positive pole powder and conductive black in the through hole and/or blind hole
Close layer.
The plus plate current-collecting body is a kind of micropore aluminium foil, and material is battery micropore aluminium foil, and battery micropore aluminium foil is often put down
There are 1000-1500 diameters in the through hole of 10-15 μm of size unevenness and 1000-3000 diameters in 10-50 μ on square centimetre
The blind hole of m sizes unevenness, each through hole and blind hole are irregular shape, and each hole is irregular roundness with aluminium foil surface junction
Arc transition, and the diameter on different directions is different；The upper and lower surface of aluminium foil is dispersed with the deep mixed indentation of multiple length simultaneously,
Indentation is 1-3 μm deep, 1-5 μm wide, and long 100-1000 μm are differed, and the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μ also can be selected
M, 16 μm, 20 μm etc..
Battery micropore aluminium foil is made of chemical liquids heat erosion method, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 30g/L
The Na of NaOH, 70g/L2CO3, 40g/L Na3PO4, the temperature of the first cleaning solution is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Paper tinsel is by the first cleaning solution, the time 10s kept in the first cleaning solution.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 1.5mol/L,
The BaCl of 0.3mol/L2, 0.5mol/L CaCl2, 0.5mol/L NH4The CuCl of Cl, 0.8mol/L2, 1mol/L FeCl3,
The temperature of corrosive liquid is maintained at 45 ± 2 DEG C.Residence time of the aluminium foil in the corrosive agent in 120s, in this stage, it is ensured that aluminium foil
Upper and lower surface is immersed in corrosive liquid simultaneously, and the type of flow for cycling corrosive liquid is flowed in aluminium foil upper and lower surface, with
Reaching makes upper and lower surface corrosion uniform.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is the Na for taking 0.4-0.8g/L2SO4、0.5—
The CaSO of 1g/L4, 0.1-0.3g/L citric acid, the temperature of the second cleaning solution is maintained at 45 ± 2 DEG C.In aluminium foil upper and lower surface
The second cleaning solution is sprayed using nozzle to be cleaned.
4）Brightization processing：The composition of brightening liquid is 5g/L CrO3、7g/L Na2Cr2O7•2H2O, 1.5g/L NaF are bright
The temperature of liquid 1 is maintained at 45 ± 2 DEG C.Surface brightening processing is carried out to the aluminium foil after cleaning.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution, the
The temperature of two cleaning solutions is maintained at 45 ± 2 DEG C.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 300 DEG C.
7）Finished product is wound.
Embodiment 5
A kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, the pole afflux
Body at least one side is coated with the composite bed of bonding agent, positive pole powder and conductive black, the positive pole powder or for ternary material,
Or it is LiFePO4 or is cobalt acid lithium；There is answering for bonding agent, positive pole powder and conductive black in the through hole and/or blind hole
Close layer.
The plus plate current-collecting body is a kind of micropore aluminium foil, and material is battery micropore aluminium foil, and battery micropore aluminium foil is often put down
There are 1000-1500 diameters in the through hole of 10-15 μm of size unevenness and 1000-3000 diameters in 10-50 μ on square centimetre
The blind hole of m sizes unevenness, each through hole and blind hole are irregular shape, and each hole is irregular roundness with aluminium foil surface junction
Arc transition, and the diameter on different directions is different；The upper and lower surface of aluminium foil is dispersed with the deep mixed indentation of multiple length simultaneously,
Indentation is 1-3 μm deep, 1-5 μm wide, and long 100-1000 μm are differed, and the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μ also can be selected
M, 16 μm, 20 μm etc..
Battery micropore aluminium foil is made of chemical liquids caustic solution, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 17g/L
The Na of NaOH, 40g/L2CO3, 25g/L Na3PO4, by the aluminium foil after rolling by the first cleaning solution, in the first cleaning solution
The time 15s of holding.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 1mol/L,
The BaCl of 0.2mol/L2, 0.3mol/L CaCl2, 0.3mol/L NH4The CuCl of Cl, 0.45mol/L2, 0.55mol/L
FeCl3, residence time of the aluminium foil in the corrosive agent in 70s, in this stage, it is ensured that aluminium foil upper and lower surface is immersed in corrosion simultaneously
In liquid, and the type of flow for cycling corrosive liquid is flowed in aluminium foil upper and lower surface, makes upper and lower surface corrosion uniform to reach.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is the Na for taking 0.4-0.8g/L2SO4、0.5—
The CaSO of 1g/L4, 0.1-0.3g/L citric acid, aluminium foil upper and lower surface using nozzle spray the second cleaning solution carry out it is clear
It washes.
4）Brightization processing：The composition of brightening liquid is 3.5g/L CrO3、4g/L Na2Cr2O7•2H2O, 0.8g/L NaF are right
Aluminium foil after cleaning carries out surface brightening processing.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 250 DEG C.
7）Finished product is wound.
Embodiment 6
A kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, the pole afflux
Body at least one side is coated with the composite bed of bonding agent, positive pole powder and conductive black, the positive pole powder or for ternary material,
Or it is LiFePO4 or is cobalt acid lithium；There is answering for bonding agent, positive pole powder and conductive black in the through hole and/or blind hole
Close layer.
The plus plate current-collecting body is a kind of micropore aluminium foil, and material is battery micropore aluminium foil, and battery micropore aluminium foil is often put down
There are 1000-1500 diameters in the through hole of 10-15 μm of size unevenness and 1000-3000 diameters in 10-50 μ on square centimetre
The blind hole of m sizes unevenness, each through hole and blind hole are irregular shape, and each hole is irregular roundness with aluminium foil surface junction
Arc transition, and the diameter on different directions is different；The upper and lower surface of aluminium foil is dispersed with the deep mixed indentation of multiple length simultaneously,
Indentation is 1-3 μm deep, 1-5 μm wide, and long 100-1000 μm are differed, and the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μ also can be selected
M, 16 μm, 20 μm etc..
Battery micropore aluminium foil is made of electrochemistry corrosion method, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 17g/L
The Na of NaOH, 40g/L2CO3, 25g/L Na3PO4, by the aluminium foil after rolling by the first cleaning solution, in the first cleaning solution
The time 15s of holding.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 1mol/L,
The BaCl of 0.2mol/L2, 0.3mol/L CaCl2, 0.3mol/L NH4The CuCl of Cl, 0.45mol/L2, 0.55mol/L
FeCl3, using etching tank as cathode, aluminium foil is corroded as anode, additional 24V direct currents.Aluminium foil is in the corrosive agent
Residence time in 70s, in this stage, it is ensured that aluminium foil upper and lower surface is immersed in corrosive liquid simultaneously, and makes corrosive liquid to cycle
The type of flow flowed in aluminium foil upper and lower surface, make upper and lower surface corrosion uniform to reach.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is to take 0.4-0.8g/LNa2SO4、0.5—
1g/LCaSO4, 0.1-0.3g/L citric acids, aluminium foil upper and lower surface using nozzle spray the second cleaning solution cleaned.
4）Brightization processing：The composition of brightening liquid is the CrO of 3.5g/L3, 4g/L Na2Cr2O7•2H2O, 0.8g/L
NaF carries out surface brightening processing to the aluminium foil after cleaning.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 250 DEG C.
7）Finished product is wound.
Embodiment 7
A kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black, the pole afflux
Body at least one side is coated with the composite bed of bonding agent, positive pole powder and conductive black, the positive pole powder or for ternary material,
Or it is LiFePO4 or is cobalt acid lithium；There is answering for bonding agent, positive pole powder and conductive black in the through hole and/or blind hole
Close layer.
The plus plate current-collecting body is a kind of micropore aluminium foil, and material is battery micropore aluminium foil, and battery micropore aluminium foil is often put down
There are 1000-1500 diameters in the through hole of 10-15 μm of size unevenness and 1000-3000 diameters in 10-50 μ on square centimetre
The blind hole of m sizes unevenness, each through hole and blind hole are irregular shape, and each hole is irregular roundness with aluminium foil surface junction
Arc transition, and the diameter on different directions is different；The upper and lower surface of aluminium foil is dispersed with the deep mixed indentation of multiple length simultaneously,
Indentation is 1-3 μm deep, 1-5 μm wide, and long 100-1000 μm are differed, and the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μ also can be selected
M, 16 μm, 20 μm etc..
Micropore aluminium foil is made of electrochemistry liquid heat erosion method, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 30g/L
The Na of NaOH, 70g/L2CO3, 40g/L Na3PO4, the temperature of the first cleaning solution is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Paper tinsel is by the first cleaning solution, the time 10s kept in the first cleaning solution.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：1.5mol/L NaCl、
0.3mol/L BaCl2、0.5mol/L CaCl2、0.5mol/L NH4Cl、0.8mol/L CuCl2、1mol/L FeCl3, corrosion
Slot is corroded as cathode, aluminium foil as anode, additional 24V direct currents.The temperature of corrosive liquid is maintained at 45 ± 2 DEG C.Aluminium foil
Residence time in the corrosive agent in 120s, in this stage, it is ensured that aluminium foil upper and lower surface is immersed in corrosive liquid simultaneously, and
The type of flow for making corrosive liquid to cycle is flowed in aluminium foil upper and lower surface, makes upper and lower surface corrosion uniform to reach.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is the Na for taking 0.4-0.8g/L2SO4、0.5—
The CaSO of 1g/L4, 0.1-0.3g/L citric acid, the temperature of the second cleaning solution is maintained at 45 ± 2 DEG C.In aluminium foil upper and lower surface
The second cleaning solution is sprayed using nozzle to be cleaned.
4）Brightization processing：The composition of brightening liquid is the CrO of 5g/L3, 7g/L Na2Cr2O7•2H2O, the NaF of 1.5g/L,
The temperature of brightening liquid is maintained at 45 ± 2 DEG C.Surface brightening processing is carried out to the aluminium foil after cleaning.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution, the
The temperature of two cleaning solutions is maintained at 45 ± 2 DEG C.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 300 DEG C.
7）Finished product is wound.
In embodiment 1-7, a kind of lithium battery anode, including：Plus plate current-collecting body, bonding agent, positive pole powder, conductive black,
The pole collector at least one side is coated with the composite bed of bonding agent, positive pole powder and conductive black, the positive pole powder
Or it is ternary material or is LiFePO4 or is cobalt acid lithium；Have in the through hole and/or blind hole bonding agent, positive pole powder and
The composite bed of conductive black.
The plus plate current-collecting body is a kind of micropore aluminium foil, and material is battery aluminium foil, and battery aluminium foil is using chemical corrosion
Method is made, different from general acid ＆ alkali liquid corrosive liquid, and chloride salt compound work also can be used in the utility model caustic solution
For corrosive liquid, the extent of reaction milder during corrosion, when aluminium foil is put into treatment fluid, under the protection of chlorion, copper
Ion or iron ion react with aluminium surface, and aluminium surface is made to form the structure of micropore, the calcium ion, sodium ion in treatment fluid with
And barium ions enters in perforated membrane and can be fixed in the follow-up process, plays a part of improvement to aluminium surface performance.It can also
Corroded using conventional acid solution and alkaline solution.Other methods are same as the prior art or similar with step, just not
It is repeating.
It is the resistivity of micropore aluminium foil and mechanical performance data table below：
Table 1 is the micropore battery aluminium foil of the utility model making and being compared as follows for primary aluminum paper tinsel resistivity：
Table 2 is as follows for the micropore battery aluminium foil of the utility model making and the comparison of primary aluminum foil dynamic performance：
By Tables 1 and 2 it can be seen that：Before relatively corroding after metallic material corrosion：Average resistivity increases by 1-3%, averagely
Tensile strength promotes 0-2%, is averagely broken breaking elongation and promotes 0-21%.
By a kind of embodiment 1-7 any one of lithium battery anode of the utility model, material is battery aluminium foil, makes aluminium
Paper tinsel collector is assembled into lithium ion battery, and the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；Micropore aluminium foil
Resistivity is increased only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses ternary material,
Since micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, the property such as capacity and charge-discharge characteristics of battery can be made
The uniformity of energy is substantially improved, and battery production yield rate improves 15-20%.
A kind of preparation method of lithium battery anode, including preparing anode collection using the method for chemical corrosion metal material
Body can refer to the method described in embodiment 1-7, and corrosive liquid is salt, without acid or alkaline solution；It can also use conventional
Acid solution or alkaline solution corroded, after metallic material corrosion relatively corrode before：Average resistivity increases by 1-3%, puts down
Equal tensile strength promotes 0-2%, is averagely broken breaking elongation and promotes 0-21%.
In addition, using a kind of use of the lithium battery anode of the utility model as lithium ion battery, since micropore aluminium foil has
There are the through hole of 10-50 μm of particular size and/or blind hole and indentation, lithium ion realization can be made to be passed through between aluminium foil, promote lithium battery
Capacity；Make micropore aluminium foil surface smoothness higher, be irregular roundness without overlap, burr, and hole and aluminium foil surface junction
Arc transition, there is no 90 ° of right angles, can effectively prevent the appearance of Li dendrite in charge and discharge process, extend the service life of battery；
In addition, micro-pore shape is also different, the hole on micropore aluminium foil obtained by chemical corrosion method is in irregular shape, aperture size
Change within the specific limits, the diameter of each hole is also varied from different directions, and the hole of this irregular shape is more
Be conducive to improve the cohesive force between aluminium foil and anode sizing agent.And existing production technology is varied without, easy to spread, it was both applicable in
Dual coating is also applied in single side coating.
Compared with primary battery aluminium foil, the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；Micropore aluminium foil
Resistivity is increased only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses ternary material,
Since micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, the property such as capacity and charge-discharge characteristics of battery can be made
The uniformity of energy is substantially improved, and battery production yield rate improves 15-20%.
Using a kind of lithium battery anode of the utility model be also used as capacitance electrode use, due to its it is every square centimeter on
It is distributed with 1000-1500 a diameter of 10-50 μm of through hole, thickness is 8-20 μm, on micropore metal material is every square centimeter
1000-3000 a diameter of 10-50 μm of blind hole is distributed with, upper and lower surface is dispersed with indentation, and indentation is wide to be 1-3 μm deep
1-5 μm, micropore metal material exists with a large amount of micropores, can promote the reserve of electricity of capacitance electrode, and material can select metallic copper
Paper tinsel or metal alloy are battery copper foil etc..
The above content is the further descriptions done with reference to specific preferred embodiment to the utility model, it is impossible to
Assert that specific embodiment of the present utility model is only limitted to this, for the utility model person of an ordinary skill in the technical field
For, on the premise of the utility model is not departed from, several simple deduction or replace can also be made, should be all considered as belonging to
The utility model determines scope of patent protection by the claims submitted.
Claims (5)
1. a kind of lithium battery anode, including：Plus plate current-collecting body（1）, bonding agent, positive pole powder, conductive black, it is characterised in that：
Composite bed of the plus plate current-collecting body at least one side coated with bonding agent, positive pole powder and conductive black composition（2）,
The plus plate current-collecting body（1）For a kind of micropore aluminium foil, the micropore aluminium foil is dispersed with multiple through holes（3）It is and/or more
A blind hole（4）；
The composite bed being made of in the through hole and/or blind hole bonding agent, positive pole powder and conductive black（2）.
2. a kind of lithium battery anode according to claim 1, it is characterised in that：The upper and lower surface of the micropore aluminium foil point
Cloth multiple indentations.
3. a kind of lithium battery anode according to claim 1, it is characterised in that：The plus plate current-collecting body dual coating has
The composite bed of bonding agent, positive pole powder and conductive black composition（2）.
4. according to a kind of lithium battery anode described in claim 1-3 any one, it is characterised in that the through hole（3）With it is blind
Hole（4）For irregular shape, and it is irregular arc transition with micropore aluminium foil surface junction.
5. according to a kind of lithium battery anode described in claim 1-3 any one, it is characterised in that：The positive pole powder or
For ternary material or it is LiFePO4 or is cobalt acid lithium.
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| CN114628077A (en) * | 2021-02-02 | 2022-06-14 | 骆驼集团新能源电池有限公司 | Porous water-based coating aluminum foil and special water-based conductive slurry thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114628077A (en) * | 2021-02-02 | 2022-06-14 | 骆驼集团新能源电池有限公司 | Porous water-based coating aluminum foil and special water-based conductive slurry thereof |
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