A kind of manufacture craft and plus plate current-collecting body of aluminium foil
Technical field
The present invention relates to aluminium foil technical fields, and in particular to a kind of manufacture craft and plus plate current-collecting body of aluminium foil.
Background technique
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, improving battery core energy storage density is the target that the whole world is pursued, and battery core energy density mentions
Height depends on the progress of its positive and negative electrode material, but also bonds 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 diaphragm is related.
Positive mix (the ferric phosphate that the collector that the anode of lithium ion battery uses is generally aluminium foil and is coated on
Lithium, cobalt acid lithium or ternary material) it is formed.The aluminium foil that traditional current collector material generally selects surface smooth, using 99 .7%
The aluminium foil of purity directly applies and is covered with active material, but the combination between the smooth aluminium foil and active material in surface more relaxes, right
Raw material and auxiliary material quality and technique require height, and active material is easy to happen in processing and charge and discharge process and falls off or loses powder existing
As reducing cycle charge discharge electrical efficiency and battery life, improving the contact resistance between component, cause under positive plate electric conductivity
Drop, to affect the comprehensive performance of battery.The serious comprehensive performance for affecting lithium ion.People generally use roughening at present
The method of aluminium foil surface increases the cohesion between aluminium foil and positive mix, but the technique can not reach desired effect.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of micropore aluminium foils
Manufacture craft, the aluminium foil and anode sizing agent layer have good caking property, and can promote the cyclicity performance of lithium battery.
The purpose of the invention is achieved by the following technical solution:
A kind of manufacture craft of aluminium foil, includes the following steps:
(1) aluminium foil surface is cleaned with deionized water;
(2) aluminium foil is subjected to exchange energization and is soaked in acid medium, ultrasonic vibration is carried out to acid medium in soaking process,
Etching time is 10-14min;
Wherein, the acid medium be aqueous solution, the component including following concentration:
HCl 0.4-0.6mol/L
H2SO4 0.1-0.2mol/L
Acetic acid 0.01-0.03mol/L
Polyethylene glycol 0.01-0.02mol/L.
The present invention does not corrode aluminium foil using traditional bichromate, and uses hydrochloric acid-sulfuric acid composite solution, salt
Acid is stronger to the corrosive power of aluminium foil, and aluminium foil surface can be made to generate more micropore, and has passivation effect by using to aluminium
The sulfuric acid of fruit and acetic acid and polyethylene glycol with slow-release function can make the micropore generated more regular, and pore-size distribution is opposite
It is relatively narrow, and be aided with ultrasound with exchange energization action, be aluminium foil porosity with higher simultaneously, also keep preferable mechanics strong
Degree.The micropore size of aluminium foil produced by the present invention is 630-780nm, porosity 21-29%.
Preferably, the acid medium includes the component of following concentration:
HCl 0.5mol/L
H2SO4 0.15mol/L
Acetic acid 0.02mol/L
Polyethylene glycol 0.015mol/L.
Wherein, the current density of the aluminium foil in the step (2) is 0.3-0.5A/cm2, a-c cycle 20-30Hz.
Wherein, in the step (2), the temperature of acid medium is maintained at 40-50 DEG C.
Wherein, in the step (2), the frequency of ultrasonic vibration is 20-30kHz.
The present invention can effectively control the surface topography of aluminium foil, make aluminium foil by the terms and conditions of control electrochemical corrosion
With preferable electrical property and mechanical property.
Wherein, the component of the aluminium foil is as follows:
Fe 1.1-1.5wt%
Mg 0.9-1.3wt%
Cu 0.01-0.05wt%
Sn 0.02-0.04wt%
Ti 0.01-0.03wt%
Remaining is Al and inevitable impurity.
The present invention optimizes the composition of aluminium foil, improves the dosage of Mg, Sn and Ti, can increase the porosity of aluminium foil, is conducive to just
Attachment of the pole slurry on aluminium foil, and improve the cycle performance of lithium battery.
Preferably, the component of the aluminium foil is as follows:
Fe 1.3wt%
Mg 1.1wt%
Cu 0.03wt%
Sn 0.03wt%
Ti 0.02wt%
Remaining is Al and inevitable impurity.
A kind of plus plate current-collecting body is made of aluminium foil as described above and the anode sizing agent layer coated on aluminium foil surface.
The anode sizing agent layer is solidified by the coating of positive-active slurry, and the positive-active slurry includes following weight
The component of number:
40-60 parts of positive active material
10-16 parts of silicon-carbon microballoon
1-2 parts of binder
40-60 parts of N- crassitude;
Wherein, the preparation method of the silicon-carbon microballoon includes the following steps:
A, the polyacrylonitrile of the nano silica fume of 2-6 parts by weight and 10-20 parts by weight is added to the dimethyl formyl of 100 parts by weight
It in amine, stirs evenly, obtains mixed solution;
B, the mixed solution is subjected to electrostatic spray, obtains silicon-organic matter microballoon;
C, the silicon-organic matter microballoon is subjected to high temperature cabonization to get the silicon-carbon microballoon is arrived.
Wherein, the partial size of the nano silica fume is 100-140nm, and the partial size of obtained silicon-carbon microballoon is 470-540nm, than
Surface area is 230-350m2/g。
Silicon-carbon microballoon produced by the present invention has the characteristics that low partial size and high-specific surface area, and electric conductivity is splendid, and leads to
The relatively commercially available conventional silicon-carbon microballoon of silicon-carbon microballoon being carbonized after polyacrylonitrile cladding nano silica fume is crossed to be easier to be embedded in this
The aluminium foil of invention, to improve the bending resistance of compacted density and aluminium foil, the cycle performance that lithium battery is made also has greatly
It is promoted, structural stability is higher.
Wherein, the positive active material is LiNixCoyMn(1-x-y)O2, y≤1, x+y≤1.
Wherein, the supply voltage of the electrostatic spray is 80-120kV, and nozzle is 15-25cm at a distance from receiver board.This
Invention can control the precipitation state of polyacrylonitrile, by the actual conditions of control electrostatic spray conducive to the uniform of nano silica fume
With polyacrylonitrile, the silicon-carbon microballoon after carbonization has the characteristics that low partial size and high-specific surface area, is easy to be embedded in the present invention for distribution
Aluminium foil obtained.
Wherein, the actual conditions of the high temperature cabonization are as follows: be warming up to 250-300 DEG C with the heating rate of 2-4 DEG C/min, protect
Warm 0.5-1.5h is warming up to 900-1100 DEG C with the heating rate of 8-10 DEG C/min, keeps the temperature 4-6h.The present invention passes through control high temperature
The actual conditions of carbonization can control the surface topography of silicon-carbon microballoon, it is not easy to there is a phenomenon where casing rupture, silicon-carbon microballoon
Structural integrity has preferable electric conductivity.
Wherein, the binder is polyvinyl alcohol and/or carboxymethyl cellulose.Preferably, the binder is carboxymethyl
Cellulose can be improved anode sizing agent in the adhesion of aluminium foil, improve the bending resistance of negative current collector.
The beneficial effects of the present invention are: the present invention does not corrode aluminium foil using traditional bichromate, and adopts
With hydrochloric acid-sulfuric acid composite solution, hydrochloric acid is stronger to the corrosive power of aluminium foil, and aluminium foil surface can be made to generate more micropore, and
By using the sulfuric acid to aluminium with passivation effect and acetic acid and polyethylene glycol with slow-release function, the micropore generated can be made
It is more regular, pore-size distribution relative narrower, and be aided with ultrasound with exchange energization action, be that aluminium foil porosity with higher is same
When, also keep preferable mechanical strength.The micropore size of aluminium foil produced by the present invention is 630-780nm, porosity 21-29%.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of manufacture craft of aluminium foil, includes the following steps:
(1) aluminium foil surface is cleaned with deionized water;
(2) aluminium foil is subjected to exchange energization and is soaked in acid medium, ultrasonic vibration is carried out to acid medium in soaking process,
Etching time is 12min;
Wherein, the acid medium be aqueous solution, the component including following concentration:
HCl 0.5mol/L
H2SO4 0.15mol/L
Acetic acid 0.02mol/L
Polyethylene glycol 0.015mol/L.
Wherein, the current density of the aluminium foil in the step (2) is 0.4A/cm2, a-c cycle 25Hz.
Wherein, in the step (2), the temperature of acid medium is maintained at 45 DEG C.
Wherein, in the step (2), the frequency of ultrasonic vibration is 25kHz.
Wherein, the component of the aluminium foil is as follows:
Fe 1.3wt%
Mg 1.1wt%
Cu 0.03wt%
Sn 0.03wt%
Ti 0.02wt%
Remaining is Al and inevitable impurity.
The micropore size of aluminium foil made from the present embodiment is 690nm, porosity 25%
Embodiment 2
A kind of manufacture craft of aluminium foil, includes the following steps:
(1) aluminium foil surface is cleaned with deionized water;
(2) aluminium foil is subjected to exchange energization and is soaked in acid medium, ultrasonic vibration is carried out to acid medium in soaking process,
Etching time is 10min;
Wherein, the acid medium be aqueous solution, the component including following concentration:
HCl 0.4mol/L
H2SO4 0.1mol/L
Acetic acid 0.01mol/L
Polyethylene glycol 0.01mol/L.
Wherein, the current density of the aluminium foil in the step (2) is 0.3A/cm2, a-c cycle 20Hz.
Wherein, in the step (2), the temperature of acid medium is maintained at 40 DEG C.
Wherein, in the step (2), the frequency of ultrasonic vibration is 20kHz.
Wherein, the component of the aluminium foil is as follows:
Fe 1.1wt%
Mg 0.9wt%
Cu 0.01wt%
Sn 0.02wt%
Ti 0.01wt%
Remaining is Al and inevitable impurity.
The micropore size of aluminium foil made from the present embodiment is 630nm, porosity 29%.
Embodiment 3
A kind of manufacture craft of aluminium foil, includes the following steps:
(1) aluminium foil surface is cleaned with deionized water;
(2) aluminium foil is subjected to exchange energization and is soaked in acid medium, ultrasonic vibration is carried out to acid medium in soaking process,
Etching time is 14min;
Wherein, the acid medium be aqueous solution, the component including following concentration:
HCl 0.6mol/L
H2SO4 0.2mol/L
Acetic acid 0.03mol/L
Polyethylene glycol 0.02mol/L.
Polyethylene glycol 0.015mol/L.
Wherein, the current density of the aluminium foil in the step (2) is 0.5A/cm2, a-c cycle 30Hz.
Wherein, in the step (2), the temperature of acid medium is maintained at 50 DEG C.
Wherein, in the step (2), the frequency of ultrasonic vibration is 30kHz.
Wherein, the component of the aluminium foil is as follows:
Fe 1.5wt%
Mg 1.3wt%
Cu 0.05wt%
Sn 0.04wt%
Ti 0.03wt%
Remaining is Al and inevitable impurity.
The micropore size of aluminium foil made from the present embodiment is 780nm, porosity 21%
Embodiment 4
A kind of plus plate current-collecting body is formed by the aluminium foil of embodiment 1 and with anode sizing agent layer coated on aluminium foil surface.
The anode sizing agent layer is solidified by the coating of positive-active slurry, and the positive-active slurry includes following weight
The component of number:
50 parts of positive active material
13 parts of silicon-carbon microballoon
1.5 parts of binder
50 parts of N- crassitude;
Wherein, the preparation method of the silicon-carbon microballoon includes the following steps:
A, the polyacrylonitrile of the nano silica fume of 4 parts by weight and 15 parts by weight is added in the dimethylformamide of 100 parts by weight,
It stirs evenly, obtains mixed solution;
B, the mixed solution is subjected to electrostatic spray, obtains silicon-organic matter microballoon;
C, the silicon-organic matter microballoon is subjected to high temperature cabonization to get the silicon-carbon microballoon is arrived.
Wherein, the partial size of the nano silica fume is 120nm, and the partial size of obtained silicon-carbon microballoon is 501.2nm, specific surface area
For 241.2m2/g。
Wherein, the positive active material is LiNixCoyMn(1-x-y)O2, y≤1, x+y≤1.
Wherein, the supply voltage of the electrostatic spray is 100kV, and nozzle is 20cm at a distance from receiver board.
Wherein, the actual conditions of the high temperature cabonization are as follows: be warming up to 275 DEG C with the heating rate of 2-4 DEG C/min, heat preservation
1h is warming up to 1000 DEG C with the heating rate of 9 DEG C/min, keeps the temperature 5h.
Wherein, the binder is carboxymethyl cellulose.
Embodiment 5
A kind of plus plate current-collecting body is formed by the aluminium foil of embodiment 1 and with anode sizing agent layer coated on aluminium foil surface.
The anode sizing agent layer is solidified by the coating of positive-active slurry, and the positive-active slurry includes following weight
The component of number:
40 parts of positive active material
10 parts of silicon-carbon microballoon
1 part of binder
40 parts of N- crassitude;
Wherein, the preparation method of the silicon-carbon microballoon includes the following steps:
A, the polyacrylonitrile of the nano silica fume of 2 parts by weight and 10 parts by weight is added in the dimethylformamide of 100 parts by weight,
It stirs evenly, obtains mixed solution;
B, the mixed solution is subjected to electrostatic spray, obtains silicon-organic matter microballoon;
C, the silicon-organic matter microballoon is subjected to high temperature cabonization to get the silicon-carbon microballoon is arrived.
Wherein, the partial size of the nano silica fume is 100nm, and the partial size of obtained silicon-carbon microballoon is 470nm, and specific surface area is
350m2/g。
Wherein, the positive active material is LiNixCoyMn(1-x-y)O2, y≤1, x+y≤1.
Wherein, the supply voltage of the electrostatic spray is 80kV, and nozzle is 15cm at a distance from receiver board.
Wherein, the actual conditions of the high temperature cabonization are as follows: be warming up to 250 DEG C with the heating rate of 2 DEG C/min, heat preservation
0.5h is warming up to 900 DEG C with the heating rate of 8 DEG C/min, keeps the temperature 4h.
Wherein, the binder is carboxymethyl cellulose.
Embodiment 6
A kind of plus plate current-collecting body is formed by the aluminium foil of embodiment 1 and with anode sizing agent layer coated on aluminium foil surface.
The anode sizing agent layer is solidified by the coating of positive-active slurry, and the positive-active slurry includes following weight
The component of number:
60 parts of positive active material
16 parts of silicon-carbon microballoon
2 parts of binder
60 parts of N- crassitude;
Wherein, the preparation method of the silicon-carbon microballoon includes the following steps:
A, the polyacrylonitrile of the nano silica fume of 6 parts by weight and 20 parts by weight is added in the dimethylformamide of 100 parts by weight,
It stirs evenly, obtains mixed solution;
B, the mixed solution is subjected to electrostatic spray, obtains silicon-organic matter microballoon;
C, the silicon-organic matter microballoon is subjected to high temperature cabonization to get the silicon-carbon microballoon is arrived.
Wherein, the partial size of the nano silica fume is 140nm, and the partial size of obtained silicon-carbon microballoon is 540nm, and specific surface area is
230m2/g。
Wherein, the positive active material is LiNixCoyMn(1-x-y)O2, y≤1, x+y≤1.
Wherein, the supply voltage of the electrostatic spray is 120kV, and nozzle is 25cm at a distance from receiver board.
Wherein, the actual conditions of the high temperature cabonization are as follows: be warming up to 300 DEG C with the heating rate of 4 DEG C/min, heat preservation
1.5h is warming up to 1100 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 6h.
Wherein, the binder is polyvinyl alcohol.
Comparative example 1
The difference of this comparative example and embodiment 4 is: the silicon-carbon microballoon is commercially available conventional silicon-carbon microballoon.
Battery is made in the plus plate current-collecting body of embodiment 4-6 and comparative example 1, negative current collector is using lithium titanate as active matter
Matter, for electrolyte using lithium hexafluoro phosphate as lithium salts, propene carbonate is organic solvent, in 3.0V-4.5V voltage range, to battery
Carry out charge and discharge cycles, the charge and discharge under 1C multiplying power, the thickness swelling and capacity retention ratio that record battery is recycled through 400 times.
The data of record are as follows:
|
Thickness swelling (%) |
Through 400 circulation volume conservation rates (%) |
Embodiment 4 |
81.4 |
86.1 |
Embodiment 5 |
83.5 |
83.5 |
Embodiment 6 |
95.5 |
81.3 |
Comparative example 1 |
177.6 |
76.6 |
There is above-mentioned test data to compare it is found that special silicon-carbon microballoon of the invention has good attachment on special micropore aluminium foil
Property, after repeatedly recycling, it is not easy to expansion drop, and the circulation volume retention property of lithium battery is effectively improved, it mentions
The high durability of lithium battery.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.