CN107768683A - A kind of high-performance lithium battery plus plate current-collecting body and its preparation method and application - Google Patents
A kind of high-performance lithium battery plus plate current-collecting body and its preparation method and application Download PDFInfo
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- CN107768683A CN107768683A CN201710929807.7A CN201710929807A CN107768683A CN 107768683 A CN107768683 A CN 107768683A CN 201710929807 A CN201710929807 A CN 201710929807A CN 107768683 A CN107768683 A CN 107768683A
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Abstract
The invention discloses a kind of high-performance lithium battery plus plate current-collecting body and its preparation method and application, belongs to lithium ion battery material technical field, and the scheme of use is：Described plus plate current-collecting body is a kind of lithium ion battery micropore aluminium foil, be distributed with described micropore aluminium foil is every square centimeter 1000-1500 a diameter of 10-50 μm through hole and/or 1000-3000 a diameter of 10-50 μm of blind hole, and it is dispersed with multiple indentations in the upper and lower surface of micropore aluminium foil, described indentation for it is deep≤5 μm, it is wide≤10 μm, it is made of chemical liquids caustic solution；Application on lithium ion battery and electric capacity, it is possible to increase battery capacity and service life；The present invention can be widely applied in technical field of energy storage.
Description
Technical field
A kind of high-performance lithium battery plus plate current-collecting body of the present invention and its preparation method and application, belongs to lithium ion battery material
Technical field.
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 also the both positive and negative polarity collector with lithium ion battery, both positive and negative polarity bond
The progress of the material such as agent, electrolyte and barrier film is relevant.
The positive mix that the collector that the positive pole of lithium ion battery uses is generally aluminium foil and is coated on（Ferric phosphate
Lithium, cobalt acid lithium or ternary material）Formed.Traditional current collector material is pure using 99.7% typically from the smooth aluminium foil in surface
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 dry linting phenomenon,
Cycle charge discharge electrical efficiency and battery life are reduced, improves the contact resistance between component, causes positive plate electric conductivity to decline,
So as to have impact on the combination property of battery.The serious combination property that have impact on 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 intended effect.Just
Pole powder and aluminium foil separation problem can all occur when winding prismatic battery and during cycle charge-discharge, and then cause product to close
Lattice rate first mate reduces, service life first mate shortens and battery capacity decay is obvious, on being influenceed the most using the battery of ternary material
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 both positive and negative polarity 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, its
Reason is on original battery automatic assembly line, using such a through-hole diameter in 1mm copper foil or aluminium foil, 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. in the patent that patent publication No. is CN 103618090A and CN 103617894A it is middle using it is acid,
Alkali electroless reagent, soda acid etching processing is carried out to aluminium foil.Obtained alumina foil contact resistance reduces unobvious, and is going corruption
The mechanical strength of aluminium foil is reduced during erosion.The method of other countries' pore-forming on aluminium foil, employs rolling or laser burns
Erosion, and the present invention uses a kind of Chemical composition that containing villaumite, and micropore aluminium foil skill is prepared by salt compounds etch
Art route is entirely different, and resulting micropore aluminium foil also has special structure and performance.
The content of the invention
Overcome the deficiencies in the prior art of the present invention, it is therefore an objective to which a kind of plus plate current-collecting body and its system of high-performance lithium battery are provided
Preparation Method and application.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of high-performance lithium battery plus plate current-collecting
Body, described plus plate current-collecting body are a kind of lithium ion battery micropore aluminium foil, are distributed with described micropore aluminium foil is every square centimeter
1000-1500 a diameter of 10-50 μm of through hole and/or 1000-3000 a diameter of 10-50 μm of blind hole, and micro-
The upper and lower surface of hole aluminium foil is dispersed with multiple indentations, described indentation for it is deep≤5 μm, it is wide≤10 μm.
Further, described through hole and blind hole are irregular shape, and are irregular with micropore aluminium foil surface junction
Arc transition.
A kind of method for preparing high-performance lithium battery plus plate current-collecting body, using the method for chemical corrosion.
Further, before relatively corroding after described micropore aluminium foil corrosion：Average resistivity increase by 2-3%, average tensile is strong
Degree lifting 0-2%, averagely it is broken breaking elongation lifting≤0-21%.
A kind of application of high-performance lithium battery plus plate current-collecting body in energy storage device.
Further, the energy storage device or be lithium ion battery, or be electric capacity.
Compared with prior art the invention has the advantages that：
A kind of plus plate current-collecting body, plus plate current-collecting body are a kind of lithium ion battery micropore aluminium foil, every square li described of micropore aluminium foil
1000-1500 a diameter of 10-50 μm of through hole is distributed with rice, thickness is 8-20 μm so that two surfaces of tinsel
Both not completely through and also completely isolated, can effectively pass through the ion and or grain of smaller less than 10-50 μm of diameter
Son, and prevent major diameter ion or particle by, while do not influence the performance of material, such as：Average resistivity increase by 1-
3%, average tensile strength lifting 0-2%, averagely it is broken breaking elongation lifting 0-21%.
Further, described micropore aluminium foil it is every square centimeter on be distributed with 1000-3000 a diameter of 10-50 μm
Blind hole, indentation is dispersed with the upper and lower surface of the micropore aluminium foil, indentation is wide 1-5 μm to be deep 1-3 μm, described through hole and
Blind hole is irregular shape and is randomly distributed, and is irregular arc transition with micropore aluminium foil surface junction.Described is logical
Hole and blind hole are irregular shape, and are irregular arc transition with aluminium foil surface junction, and aperture size is within the specific limits
Change, the diameter of each hole are also varied from different directions.When can lift micropore aluminium foil two sides and being coated, lifting
The adhesive force of coating, through hole and blind hole and material body arc transition, reduce stress concentration, strengthen mechanical property, will not weaken
Electric property.
If there are 1000-1500 on its is every square centimeter directly as lithium battery anode collector using micropore aluminium foil
Footpath had made inside and outside micropore aluminium foil two surfaces both in the blind hole of 10-50 μm of through hole and 1000-3000 diameters at 10-50 μm
It is not completely isolated completely through yet, can be by lithium particle, and other particles or particle are prevented by the way that lithium ion passes through just
It after the collector of pole, can be moved about in whole lithium battery, improve lithium ion activity, improve battery capacity, coating is superincumbent just
Pole material and aluminium foil are integral, and its adhesive force significantly improves, and Li dendrite will not be grown at through hole and blind hole.
3rd, a kind of method for preparing positive current collector material, using the method for chemical liquids corrosive aluminum foil, can use conventional
Acid solution corrosion, conventional alkali soluble corrosion can also be used, pure salting liquid can also be used, reduced environmental pollution.
The present invention can also use chloride salt using being different from general acid ＆ alkali liquid corrosive liquid in caustic solution of the present invention
Compound is as corrosive liquid, the extent of reaction milder during corrosion, when aluminium foil is put into treatment fluid, in the protection of chlorion
Under, copper ion or iron ion react with aluminium surface, aluminium surface is formed the structure of micropore, calcium ion, sodium in treatment fluid
Ion and barium ions enter in perforated membrane and can be fixed in subsequent process, play a part of improvement to aluminium surface performance.
The size of the hole of micropore aluminium foil of the present invention is much smaller than the aperture of the micropore aluminium foil prepared by prior art, while again
Avoid hole it is too small caused by positive electrode the problem of appearance can not penetrate in aluminium foil, micropore aluminium foil of the invention due to
The hole and indentation of particular size, make micropore aluminium foil surface smoothness higher, without overlap, burr, and hole and aluminium foil surface
Junction is irregular arc transition, in the absence of 90 ° of right angles, can effectively prevent the appearance of Li dendrite in charge and discharge process, prolong
The service life of long battery；In addition, micro-pore shape is also different, the hole on micropore aluminium foil obtained by chemical corrosion method is not in
Regular shape, aperture size change within the specific limits, and the diameter of each hole is also varied from different directions, it is this not
The hole of regular shape is more beneficial for improving the cohesive force between aluminium foil and anode sizing agent.And existing production technology is varied without,
Easy to spread, it is not only suitable for one side coating and is also applied for dual coating.
Compared with galvanic cell aluminium foil, the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；Micropore aluminium foil
Resistivity increase only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses ternary material,
Because 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%.
Brief description of the drawings
Fig. 1 is the micro image of the embodiment of the present invention 1.
Fig. 2 is the stress strain curve figure of the embodiment of the present invention 1.
Fig. 3 is the micro image of the embodiment of the present invention 3.
Fig. 4 is the stress strain curve figure of the embodiment of the present invention 3.
Fig. 5 is the micro image of the embodiment of the present invention 6.
Fig. 6 is the stress strain curve figure of the embodiment of the present invention 6.
Fig. 7 is the micro image of the embodiment of the present invention 7.
Fig. 8 is the stress strain curve figure of the embodiment of the present invention 7.
Embodiment
Embodiment 1
A kind of high-performance lithium battery plus plate current-collecting body, as shown in figure 1, the micro image of high-performance lithium battery plus plate current-collecting body, its
Material is battery micropore aluminium foil.There are 1000-1500 diameters in 10-15 μm of sizes on the battery micropore aluminium foil is every square centimeter
In the uneven blind hole of 10-50 μm of sizes, each through hole and blind hole are irregular shape for uneven through hole and 1000-3000 diameters
Shape, each hole and aluminium foil surface junction are irregular arc transition, and the diameter on different directions is different；Above and below aluminium foil
Surface is dispersed with the deep mixed indentation of multiple length simultaneously, and indentation is deep 1-3 μm, wide 1-5 μm, long 100-1000 μm,
The thickness of battery aluminium foil is 15 μm, also can be selected 10 μm, 12 μm, 16 μm, 20 μm etc..
Above-mentioned high-performance lithium battery plus plate current-collecting body is that micropore aluminium foil is made of chemical liquids caustic solution, according to following step
It is rapid to carry out：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning fluid be 5g/L NaOH,
70g/L Na2CO3, 40g/L Na3PO4, by the aluminium foil after rolling by the first cleaning fluid, kept in the first cleaning fluid
Time be 6s.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：0.5mol/L NaCl,
0.1mol/L BaCl2, 0.1mol/L CaCl2, 0.1mol/L NH4Cl, 0.1mol/L CuCl2, 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 circulating corrosive liquid flows 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 fluid 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 shower nozzle spray the second cleaning fluid cleaned.
4）Brightization processing：The composition of brightening liquid is 2g/L CrO3, 1g/L Na2Cr2O7•2H2O, 0.1g/L NaF,
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 fluid.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 200 DEG C.
7）Finished product is wound.
Fig. 1 is a kind of high-performance lithium battery plus plate current-collecting body, and its material is battery aluminium foil, the battery micropore aluminium foil it is microcosmic
Image.From Fig. 1 as can be seen that micropore aluminium foil inside and outside two surfaces both completely through and also it is completely isolated, be coated in
Positive electrode above and aluminium foil are integral, and its adhesive force significantly improves.
Fig. 2 is a kind of stress strain curve of high-performance lithium battery plus plate current-collecting body, and its material is battery aluminium foil, curve 1 in figure
For the stress strain curve of galvanic cell aluminium foil, curve 2 is the stress strain curve of battery micropore aluminium foil, the battery micropore after chemical attack
Aluminium foil, its tensile property does not reduce compared with galvanic cell aluminium foil, close on the contrary or increase.
By a kind of high-performance lithium battery plus plate current-collecting body of the present embodiment, its material is battery aluminium foil, makes aluminum foil current collector
It is assembled into lithium ion battery：8.5g LiFePO4s, 1.0g acetylene blacks and 0.5g PVDF are weighed, and adds 20g NMP, fully
Stirring makes well mixed slurry.Then scratched in the micropore aluminium foil afflux handled well through the embodiment of the present invention 1
On body, under 0.01MPa vacuum 80 DEG C of dryings to constant weight, and in 10-15MPa pressure lower rolls be pressed into LiFePO4 electricity
Pole, and it is cut into positive pole disk.Equally, 4.25g graphite, 0.5g acetylene blacks and 0.25g butadiene-styrene rubber binding agents are weighed, and is added
Enter 10g NMP, be sufficiently stirred the slurry for making well mixed, then scratched in the common copper foil cleaned through ethanol
On, it is pressed into negative plate.By positive plate, celgard2400 polypropylene porous films barrier film, negative plate lamination assembling in sequence
Into battery core, then with battery housing seal battery core, toward battery container in inject 1mol/L LiBF4/ diethyl carbonate electrolyte,
Liquid injection port is sealed 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 2.5-4.2V voltage range
Lithium ion battery carry out 1C charge-discharge tests, the specific discharge capacity of the 3rd time be 179mAh/g, progress 300 discharge and recharges follow
After ring, capability retention 95.6%.
To further illustrate beneficial effect of the present invention, spy sets following comparative example：
8.5g LiFePO4s, 1.0g acetylene blacks and 0.5g PVDF are weighed, and adds 20g NMP, is sufficiently stirred and makes mixed
Close uniform slurry.Then scratched in the normal aluminium foil cleaned through ethanol, done for 80 DEG C under 0.01MPa vacuum
It is dry to be pressed into iron phosphate lithium electrode to constant weight, and in 10-15MPa pressure lower rolls, and it is cut into positive pole disk.Equally, weigh
4.25g graphite, 0.5g acetylene blacks and 0.25g butadiene-styrene rubber binding agents, and 10g NMP are added, it is sufficiently stirred and makes mixed
Uniform slurry is closed, is then scratched on the common copper foil cleaned through ethanol, 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 barrier film, negative plate
Core, toward battery container 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, capability retention is lithium ion battery obtained by the comparative example
82.5%.As can be seen here, micropore aluminum foil current collector made from the present embodiment, because 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 life-span.
A kind of micropore aluminium foil of high-performance lithium battery plus plate current-collecting body of the present invention is made due to the hole and indentation of particular size
Micropore aluminium foil surface smoothness is higher, is irregular arc transition without overlap, burr, and hole and aluminium foil surface junction,
In the absence of 90 ° of right angles, the appearance of Li dendrite in charge and discharge process can be effectively prevented, extends the service life of battery；It is in addition, micro-
Hole shape is also different, and the hole on micropore aluminium foil obtained by chemical corrosion method is in irregular shape, and aperture size is certain
In the range of change, the diameter of each hole is also varied from different directions, and the hole of this irregular shape is more beneficial for
Improve the cohesive force between aluminium foil and anode sizing agent.And existing production technology is varied without, easy to spread, it is not only suitable for one side
Coating is also applied for dual coating.
Compared with galvanic cell aluminium foil, the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；Micropore aluminium foil
Resistivity increase only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses ternary material,
Because 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 high-performance lithium battery plus plate current-collecting body, its material are battery aluminium foil, are had on the battery micropore aluminium foil is every square centimeter
1000-1500 diameters are in the uneven through hole of 10-15 μm of sizes and 1000-3000 diameters in 10-50 μm of size inequalities
Blind hole, each through hole and blind hole are irregular shape, and each hole and aluminium foil surface junction are irregular arc transition, and
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, and indentation deep 1-
3 μm, wide 1-5 μm, long 100-1000 μm, the thickness of battery aluminium foil is 15 μm, also can be selected 10 μm, 12 μm, 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 fluid is 30g/L
NaOH, 70g/L Na2CO3, 40g/L Na3PO4, by the aluminium foil after rolling by the first cleaning fluid, in the first cleaning fluid
The time 10s of holding.
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, 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
Lose in liquid, and the type of flow for circulating corrosive liquid flows 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 fluid 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 shower nozzle spray the second cleaning fluid 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 fluid.
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 high-performance lithium battery plus plate current-collecting body, its material are battery micropore aluminium foil, on battery micropore aluminium foil is every square centimeter
Have 1000-1500 diameters the uneven through hole of 10-15 μm of sizes and 1000-3000 diameters in 10-50 μm of sizes not
Equal blind hole, each through hole and blind hole are irregular shape, and each hole and aluminium foil surface junction are irregular 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, and indentation is deep
1-3 μm, wide 1-5 μm, long 100-1000 μm, the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μm, 16 μ also can be selected
M, 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 fluid is 17g/L
NaOH, 40g/L Na2CO3, 25g/L Na3PO4, the temperature of the first cleaning fluid is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Paper tinsel is by the first cleaning fluid, the time 15s kept in the first cleaning fluid.
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 circulating corrosive liquid flows 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 fluid 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 fluid is maintained at 45 ± 2 DEG C.Make in aluminium foil upper and lower surface
The second cleaning fluid is sprayed with shower 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 fluid, the
The temperature of two cleaning fluids 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.
Fig. 3 is a kind of micropore metal material, and its material is battery aluminium foil, the micro image of the battery micropore aluminium foil.From Fig. 1
In as can be seen that micropore aluminium foil inside and outside two surfaces both completely through and also it is completely isolated, coat superincumbent positive pole
Material is integral with aluminium foil, and its adhesive force significantly improves.
Fig. 4 is a kind of stress strain curve of micropore metal material, and its material is battery aluminium foil, and curve 1 is galvanic cell aluminium in figure
The stress strain curve of paper tinsel, curve 2 are the stress strain curve of battery micropore aluminium foil, and the battery micropore aluminium foil after chemical attack, it draws
Stretch performance does not reduce compared with galvanic cell aluminium foil, close on the contrary or increase.
Embodiment 4
A kind of high-performance lithium battery plus plate current-collecting body, its material are battery micropore aluminium foil, on battery micropore aluminium foil is every square centimeter
Have 1000-1500 diameters the uneven through hole of 10-15 μm of sizes and 1000-3000 diameters in 10-50 μm of sizes not
Equal blind hole, each through hole and blind hole are irregular shape, and each hole and aluminium foil surface junction are irregular 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, and indentation is deep
1-3 μm, wide 1-5 μm, long 100-1000 μm, the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μm, 16 μ also can be selected
M, 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 fluid is 30g/L
NaOH, 70g/L Na2CO3, 40g/L Na3PO4, the temperature of the first cleaning fluid is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Paper tinsel is by the first cleaning fluid, the time 10s kept in the first cleaning fluid.
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,
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 circulating corrosive liquid flows 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 fluid is the Na for taking 0.4-0.8g/L2SO4、0.5—
1g/L CaSO4, 0.1-0.3g/L citric acid, the temperature of the second cleaning fluid is maintained at 45 ± 2 DEG C.In aluminium foil upper and lower surface
The second cleaning fluid is sprayed using shower 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 fluid, the
The temperature of two cleaning fluids 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 high-performance lithium battery plus plate current-collecting body, its material are battery micropore aluminium foil, on battery micropore aluminium foil is every square centimeter
Have 1000-1500 diameters the uneven through hole of 10-15 μm of sizes and 1000-3000 diameters in 10-50 μm of sizes not
Equal blind hole, each through hole and blind hole are irregular shape, and each hole and aluminium foil surface junction are irregular 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, and indentation is deep
1-3 μm, wide 1-5 μm, long 100-1000 μm, the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μm, 16 μ also can be selected
M, 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 fluid is 17g/L
NaOH, 40g/L Na2CO3, 25g/L Na3PO4, by the aluminium foil after rolling by the first cleaning fluid, in the first cleaning fluid
The time 15s of holding.
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/L CuCl2, 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 circulating corrosive liquid flows 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 fluid is the Na for taking 0.4-0.8g/L2SO4、0.5—
1g/L CaSO4, 0.1-0.3g/L citric acid, aluminium foil upper and lower surface using shower nozzle spray the second cleaning fluid carry out it is clear
Wash.
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 fluid.
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 high-performance lithium battery plus plate current-collecting body, its material are battery micropore aluminium foil, on battery micropore aluminium foil is every square centimeter
Have 1000-1500 diameters the uneven through hole of 10-15 μm of sizes and 1000-3000 diameters in 10-50 μm of sizes not
Equal blind hole, each through hole and blind hole are irregular shape, and each hole and aluminium foil surface junction are irregular 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, and indentation is deep
1-3 μm, wide 1-5 μm, long 100-1000 μm, the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μm, 16 μ also can be selected
M, 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 fluid is 17g/L
NaOH, 40g/L Na2CO3, 25g/L Na3PO4, by the aluminium foil after rolling by the first cleaning fluid, in the first cleaning fluid
The time 15s of holding.
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/L CuCl2, 0.55mol/L
FeCl3, corroded using etching tank as negative electrode, aluminium foil as anode, additional 24V direct currents.Aluminium foil is in the corrosive agent
Residence time in 70s, in this stage simultaneously, it is ensured that aluminium foil upper and lower surface is immersed in corrosive liquid, and makes corrosive liquid to circulate
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 fluid 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 shower nozzle spray the second cleaning fluid cleaned.
4）Brightization processing：The composition of brightening liquid is 3.5g/L CrO3, 4g/L Na2Cr2O7•2H2O, 0.8g/L
NaF, 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 fluid.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 250 DEG C.
7）Finished product is wound.
Fig. 5 is a kind of micropore metal material, and its material is battery aluminium foil, the micro image of the battery micropore aluminium foil.From Fig. 1
In as can be seen that micropore aluminium foil inside and outside two surfaces both completely through and also it is completely isolated, coat superincumbent positive pole
Material is integral with aluminium foil, and its adhesive force significantly improves.
Fig. 6 is a kind of stress strain curve of micropore metal material, and its material is battery aluminium foil, and curve 1 is galvanic cell aluminium in figure
The stress strain curve of paper tinsel, curve 2 are the stress strain curve of battery micropore aluminium foil, and the battery micropore aluminium foil after chemical attack, it draws
Stretch performance does not reduce compared with galvanic cell aluminium foil, close on the contrary or increase.
Embodiment 7
A kind of high-performance lithium battery plus plate current-collecting body, its material are battery micropore aluminium foil, on battery micropore aluminium foil is every square centimeter
Have 1000-1500 diameters the uneven through hole of 10-15 μm of sizes and 1000-3000 diameters in 10-50 μm of sizes not
Equal blind hole, each through hole and blind hole are irregular shape, and each hole and aluminium foil surface junction are irregular 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, and indentation is deep
1-3 μm, wide 1-5 μm, long 100-1000 μm, the thickness of battery aluminium foil is 15 μm, and 10 μm, 12 μm, 16 μ also can be selected
M, 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 fluid is 30g/L
NaOH, 70g/L Na2CO3, 40g/L Na3PO4, the temperature of the first cleaning fluid is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Paper tinsel is by the first cleaning fluid, the time 10s kept in the first cleaning fluid.
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
Groove is corroded as negative electrode, 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 circulate flows 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 fluid is the Na for taking 0.4-0.8g/L2SO4、0.5—
1g/L CaSO4, 0.1-0.3g/L citric acid, the temperature of the second cleaning fluid is maintained at 45 ± 2 DEG C.In aluminium foil upper and lower surface
The second cleaning fluid is sprayed using shower nozzle to be cleaned.
4）Brightization processing：The composition of brightening liquid is 5g/L CrO3, 7g/L Na2Cr2O7•2H2O, 1.5g/L NaF,
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 fluid, the
The temperature of two cleaning fluids 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.
Fig. 7 is a kind of micropore metal material, and its material is battery aluminium foil, the micro image of the battery micropore aluminium foil.From Fig. 1
In as can be seen that micropore aluminium foil inside and outside two surfaces both completely through and also it is completely isolated, coat superincumbent positive pole
Material is integral with aluminium foil, and its adhesive force significantly improves.
Fig. 8 is a kind of stress strain curve of micropore metal material, and its material is battery aluminium foil, and curve 1 is galvanic cell aluminium in figure
The stress strain curve of paper tinsel, curve 2 are the stress strain curve of battery micropore aluminium foil, and the battery micropore aluminium foil after chemical attack, it draws
Stretch performance does not reduce compared with galvanic cell aluminium foil, close on the contrary or increase.
In embodiment 1-7, a kind of high-performance lithium battery plus plate current-collecting body is prepared, material is battery aluminium foil, using chemical liquids
Caustic solution is made, different from general acid ＆ alkali liquid corrosive liquid, can also use chloride salt compound to make in caustic solution of the present invention
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, aluminium surface is formed 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 subsequent process, plays a part of improvement to aluminium surface performance.Can also
Corroded using the acid solution and alkaline solution of routine.
It is the resistivity and mechanical performance data table of micropore aluminium foil below：
Table 1 is being compared as follows for micropore aluminium foil and primary aluminum paper tinsel resistivity：
Table 2 is as follows for the contrast of micropore aluminium foil and primary aluminum foil dynamic performance：
By Tables 1 and 2 it can be seen that：Before relatively corroding after metallic material corrosion：Average resistivity increase by 1-3%, average tensile
Strength enhancing 0-2%, averagely it is broken breaking elongation lifting 0-21%.
By a kind of embodiment 1-7 any one of high-performance lithium battery plus plate current-collecting body of the present invention, its material is battery aluminium
Paper tinsel, make aluminum foil current collector and be assembled into lithium ion battery, the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；It is micro-
The resistivity of hole aluminium foil increase only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses three
During first material, because micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, capacity and the charge and discharge of battery can be made
The uniformity of the performances such as electrical feature is substantially improved, and battery production yield rate improves 15-20%.
A kind of preparation method of high-performance lithium battery plus plate current-collecting body, can using the method for chemical corrosion metal material
With reference to the method described in embodiment 1-7, conventional acid solution and alkaline solution can also be used to be corroded, metal material is rotten
Before relatively corroding after erosion：Average resistivity increase by 1-3%, average tensile strength lifting 0-2%, averagely it is broken breaking elongation lifting
0—21%。
In addition, made using a kind of high-performance lithium battery plus plate current-collecting body of the present invention as anode current collector of lithium ion battery
With because micropore aluminium foil has the through hole and/or blind hole and indentation of particular size, making micropore aluminium foil surface smoothness higher, not having
There are overlap, burr, and hole and aluminium foil surface junction are irregular arc transition, in the absence of 90 ° of right angles, can effectively be prevented
The appearance of Li dendrite in charge and discharge process, extend the service life of battery；In addition, micro-pore shape is also different, chemical attack
The hole on micropore aluminium foil obtained by method is in irregular shape, and aperture size changes within the specific limits, the diameter of each hole
Also it is varied from different directions, the hole of this irregular shape is more beneficial for improving viscous between aluminium foil and anode sizing agent
Tie power.And existing production technology is varied without, easy to spread, it is not only suitable for one side coating and is also applied for dual coating.
Compared with galvanic cell aluminium foil, the tensile strength of micropore aluminium foil is close with the tensile strength of primary aluminum paper tinsel；Micropore aluminium foil
Resistivity increase only can make the capacity of lithium ion battery improve 8-10% less than 3%.When positive electrode uses ternary material,
Because 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%.
Capacitance electrode is also used as using a kind of high-performance lithium battery plus plate current-collecting body of the present invention to use, because it is often put down
1000-1500 a diameter of 10-50 μm of through hole is distributed with square centimetre, thickness is 8-20 μm, and micropore metal material is often put down
Be distributed with 1000-3000 a diameter of 10-50 μm of blind hole on square centimetre, upper and lower surface is dispersed with indentation, indentation for deep 1-
3 μm, wide 1-5 μm, there are micropore metal material a large amount of micropores to exist, and can lift the reserve of electricity of capacitance electrode, and material can be selected
Metal copper foil, or metal alloy, or be battery copper foil etc..
Above content is to combine the further description that specific preferred embodiment is done to the present invention, it is impossible to is assert
The embodiment of the present invention is only limitted to this, for general technical staff of the technical field of the invention, is not taking off
On the premise of from the present invention, some simple deduction or replace can also be made, should all be considered as belonging to the present invention by being submitted
Claims determine scope of patent protection.
Claims (6)
- A kind of 1. high-performance lithium battery plus plate current-collecting body, it is characterised in that：Described plus plate current-collecting body is a kind of lithium ion battery Micropore aluminium foil, be distributed with described micropore aluminium foil is every square centimeter 1000-1500 a diameter of 10-50 μm through hole and/ Or 1000-3000 a diameter of 10-50 μm of blind hole, and multiple indentations are dispersed with the upper and lower surface of micropore aluminium foil, it is described Indentation for it is deep≤5 μm, it is wide≤10 μm.
- A kind of 2. high-performance lithium battery plus plate current-collecting body according to claim 1, it is characterised in that described through hole and blind Hole is irregular shape, and is irregular arc transition with micropore aluminium foil surface junction.
- A kind of 3. method of the high-performance lithium battery plus plate current-collecting body prepared described in claim 1 or 2, it is characterised in that useization The method for learning corrosion.
- 4. according to the method for claim 3, it is characterised in that：Before relatively corroding after described micropore aluminium foil corrosion：Average electricity Resistance rate increase by 2-3%, average tensile strength lifting 0-2%, averagely it is broken breaking elongation lifting≤0-21%.
- A kind of 5. application of plus plate current-collecting body in energy storage device as claimed in claim 1.
- A kind of 6. application of the plus plate current-collecting body according to claim 5 in energy storage device, it is characterised in that：The energy storage Device is lithium ion battery, or is electric capacity.
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| CN114744208A (en) * | 2022-03-29 | 2022-07-12 | 佛山市中技烯米新材料有限公司 | Current collector etching foil, preparation method thereof, electrode and lithium battery |
| CN115595593A (en) * | 2022-09-27 | 2023-01-13 | 上海凯矜新材料科技有限公司（Cn） | Method for removing oxide film on aluminum foil surface of lithium battery |
| CN115799443A (en) * | 2023-02-06 | 2023-03-14 | 中自环保科技股份有限公司 | Sodium ion battery microporous aluminum foil electrode and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108611676A (en) * | 2018-07-04 | 2018-10-02 | 山西沃特海默新材料科技股份有限公司 | A kind of the electrochemical corrosion preparation method and its micropore copper foil of micropore battery copper foil |
| CN114744208A (en) * | 2022-03-29 | 2022-07-12 | 佛山市中技烯米新材料有限公司 | Current collector etching foil, preparation method thereof, electrode and lithium battery |
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| CN115595593A (en) * | 2022-09-27 | 2023-01-13 | 上海凯矜新材料科技有限公司（Cn） | Method for removing oxide film on aluminum foil surface of lithium battery |
| CN115799443A (en) * | 2023-02-06 | 2023-03-14 | 中自环保科技股份有限公司 | Sodium ion battery microporous aluminum foil electrode and preparation method thereof |
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