CN108987839A - A kind of method of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation - Google Patents
A kind of method of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention relates to the methods of a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation, the following steps are included: positive plate of lithium battery is placed in clear water by (1), hydrogenperoxide steam generator, ultrasonic reaction is added, cooling, filtering, washs, is dried to obtain the cobalt acid lithium of poor lithium；(2) lithium battery cathode plate is placed in clear water, ultrasonic reaction, cooling is filtered, washed, and collects the filtrate for being rich in lithium；(3) after the cobalt acid lithium of poor lithium and the filtrate rich in lithium mix, hydrogenperoxide steam generator is added, pours into ultrasonic response kettle, is passed through cavitation gas and removes air and enhance cavitation effect, carry out ultrasonic reaction, cool down, be filtered, washed, dry after obtain the cobalt acid lithium of reconstruction reparation.Compared with prior art, the present invention can get through the recycling of lithium in cathode graphite and the supersonic, water-heating of positive cobalt acid lithium separate with reconstruction repair process, realization elemental lithium recycling in lithium battery, process is simple, strong operability.
Description
Technical field
The present invention relates to a kind of electron wastes recovery method as resource, more particularly, to a kind of pair of lithium battery anode failure cobalt
The method of sour lithium reconstruction reparation.
Background technique
Light weight, energy density is big, self discharge is small, have extended cycle life, memory-less effect, environmentally protective because having for lithium battery
Many advantages, such as, and be widely used in communicating, in portable electronic product, and expand to electric car, space flight, military affairs and intelligence
The fields such as power grid, it is growing day by day to its demand and output.After excessive charge and discharge, lithium ion battery because of its micropore surface and
Changes in crystal structure and poor lithium cause reversible energy storage chemical property to fail, and generate a large amount of waste battery therewith.Used Li ion
The exposure of the poisonous and harmful substances such as organic electrolyte and heavy metal in battery in the environment, will cause serious environmental risk.
Because of energy density with higher, it is readily produced and a series of excellent chemical properties such as persistence, cobalt acid lithium
The positive electrode active materials of large-scale commercial applications application.Because of cobalt containing rare precious metal and lithium, cost account for the 40% of battery totle drilling cost with
On, the recovery value of cobalt acid lithium is higher.From the point of view of cobalt acid lithium recycling in lithium battery industry, after its failure to its into
Row separation and purification, are then back to the preparation of lithium battery anode again, and whole process link is more, and are related to the multiple of cobalt and lithium
Conversion, overall craft is complicated and energy consumption is higher.
With being used for multiple times for lithium battery, lithium ion transition deintercalation leads to the poor lithium of cobalt acid lithium.The part lithium ion that deintercalation goes out
It is embedded into cathode graphite, so that there are the lithiums of high-content in graphite, it would be highly desirable to recycle.Meanwhile graphite is a kind of important strategy
Reserved resources are the important source materials for preparing graphene and graphene derived product.It is dual based on environmental risk and recycling
Feature, the separation of used Li ion cell, especially cobalt acid lithium and higher value application, the recycling and benefit of lithium in graphite and graphite
With, it has also become the hot spot paid close attention to both at home and abroad.
Chinese patent CN201310095245.2 discloses one kind and recycles cobalt acid lithium from cobalt acid lithium battery waste positive
Method, comprising the following steps: (1) cobalt acid lithium battery waste positive is put into the 1-2mol/L hydrochloric acid dissolved with citric acid
In leachate, 4-6h is reacted under the conditions of 60-80 DEG C；(2) leachate of step (1) is filtered, isolates aluminium foil and consolidated
Body particle；(3) solid particle is washed and is dried；(4) Co/Li mass in lithium source adjustment solid particle is added in solid particle
Than, it mixes, calcines, it is cooling, obtain cobalt acid lithium.This method makes aluminium foil surface generate defect, into one by corroding to aluminium foil
Step reduces the combination of PVDF and aluminium foil, achievees the purpose that be kept completely separate positive electrode and aluminium foil, influences the yield of aluminium foil, and
This method needs separately to add lithium source, does not recycle, results in waste of resources, in addition this method is recycled to the lithium for being lost to cathode
After cobalt acid lithium circulation electric discharge, capacity reduces more.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of device simple and behaviour
Make simple treatment process, low energy consumption, and environment influences lithium in the useless cathode of lithium battery graphite of small utilization and fails to lithium battery anode
The method of cobalt acid lithium reconstruction reparation.
The present invention is for the architectural characteristic and cobalt for passing through organic matter Kynoar (PVDF) bonding between cobalt acid lithium and aluminium foil
The sour lithium failure cause that poor lithium causes reversible energy storage chemical property to fail because of micropore surface and changes in crystal structure, based on super
Sound cavitation effect can provide transient state localized hyperthermia for chemical reaction, high pressure, pretend use and the hydroxyl radical free radical of Strong oxdiative ability etc.
Significant properties, present invention proposition separate the failure cobalt acid lithium being adhered on positive pole aluminium foil, and with adhesion deposition in cathode
Lithium in the electrolyte of graphite is lithium source, carries out reconstruction reparation to the cobalt acid lithium after separation, to realize elemental lithium in lithium electricity
Recycling in pond provides theoretical foundation for industrial upgrading.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of method of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation, comprising the following steps:
(1) positive plate of lithium battery is placed in clear water, 30% oxidants hydrogen peroxide solution is added further to remove
For PVDF to preferably separate cobalt acid lithium and aluminium foil, ultrasonic reaction, the cobalt acid lithium of poor lithium is washed, is dried to obtain in cooling, filtering；
(2) lithium battery cathode plate is placed in clear water, ultrasonic reaction is carried out after mixing, cooling is filtered, washed, and is collected rich
Filtrate containing lithium；
(3) it after the filtrate rich in lithium for obtaining the cobalt acid lithium for the poor lithium that step (1) obtains and step (2) mixes, is added
30% hydrogenperoxide steam generator pours into ultrasonic response kettle with the oxidation environment in intensified response kettle, is passed through the removing of cavitation gas
Air simultaneously enhances cavitation effect, carries out ultrasonic reaction, cool down, is filtered, washed, dry after obtain reconstruction reparation cobalt it is sour
Lithium.
Preferably, in step (1), used Li ion cell machinery is split first, anode and cathode is obtained, is shredded into
Size is 3-5cm2Fragment
Preferably, in step (1): solid-to-liquid ratio 1:140-3:70g/mL, mixeding liquid volume are the 60- of reactor volume
70%.
Preferably, in step (1): the volume ratio of the hydrogenperoxide steam generator of addition and clear water is 1:1400-1:100.
Preferably, in step (1) ultrasonic reaction process conditions are as follows: mixing speed 30-200r/min, reaction temperature are
25-75 DEG C, supersonic generator power is 90-500W, reaction time 10-150min.
Preferably, in step (2): solid-to-liquid ratio 3:100-1:20g/mL, mixeding liquid volume are the 60- of reactor volume
70%.
Preferably, in step (2) ultrasonic reaction process conditions are as follows: mixing speed 30-200r/min, reaction temperature are
75-90 DEG C, supersonic generator power is 90-500W, reaction time 60-120min.
Preferably, in step (3): the volume ratio of the hydrogenperoxide steam generator of addition and clear water is 1:400-1:50.
Preferably, in step (3): solid-to-liquid ratio is 1:100~1:40g/mL, and mixeding liquid volume is the 60- of reactor volume
70%.
Preferably, in step (3): being passed through cavitation gas 15-30min from intake valve, air outlet valve is opened simultaneously, sufficiently to catch up with
The air in kettle is walked, cavitation gas intake is controlled by control decompression table registration, after mixing up decompression table registration, closes outlet
Valve.It is furthermore preferred that the cavitation gas is argon gas, nitrogen or oxygen.
Preferably, in step (3) ultrasonic reaction process conditions are as follows: the pressure of cavitation gas be 0-0.5MPa, reaction temperature
Degree is 70-100 DEG C, and supersonic generator power is 750-1150W, reaction time 6-10h.
Preferably, the washing is washed 3-5 times using clear water, and the drying temperature is 60-80 DEG C, drying time 8-
10h。
The present invention melts cobalt acid lithium crystal using the local high temperature and high pressure environment that ultrasonic cavitation is formed, promote cobalt and
Lithium occurs cation and resets, and cobalt, lithium occupy-place are orderly, have reformed good layer structure.The mechanical effect and cavitation effect of ultrasound,
The progress for promoting lithium ion mass transfer reaction in graphite leaching lithium liquid, increases lithium ion content in cobalt acid lithium, promotes cobalt acid lithium crystal
Reformation and growth.
Efficiently separating for graphite and copper foil may be implemented in present invention process, and the rate of recovery of graphite can achieve about 100%, together
When, the structure of copper foil keeps more complete, is easy to reuse.While supersonic, water-heating separates graphite and copper foil, graphite can be removed
The lithium in graphite is recycled in the partial organic substances on surface, extraction.
Efficiently separating for cobalt acid lithium and aluminium foil may be implemented in the present invention, and the rate of recovery of cobalt acid lithium can achieve about 90%-
100%, in addition, the organic moiety on cobalt acid lithium surface removes after supersonic, water-heating reaction, be conducive to subsequent cobalt acid lithium crystal structure
Supersonic, water-heating reform repair.
The present invention can effectively get through the reconstruction reparation of the recycling of lithium and anode failure cobalt acid lithium in cathode graphite,
It realizes elemental lithium recycling in lithium battery interior, forms environmental-friendly simple process, efficient, low energy consumption useless lithium battery
Cobalt acid lithium method of resource provides new thinking for useless lithium battery disposal of resources, improves useless lithium battery resource utilization value.
Further to remove the PVDF in cobalt acid lithium surface and gap, separation and the structure weight of cobalt acid lithium is better achieved
It is whole, oxidants hydrogen peroxide solution is added in step (1) and (3).Hydrogenperoxide steam generator is anti-in the separation and reformation of cobalt acid lithium
Answer middle effect significant.When not adding hydrogen peroxide, the rate of recovery of cobalt acid lithium is only 75.69% in step (1)；As addition 1-
When 6mL hydrogen peroxide, the rate of recovery of cobalt acid lithium is higher than 95% in step (1).
Cavitation gas is dissolved in the gas in solution, and cavitation effect can be improved.The type of solution cavitation gas and contain
Amount is affected to ultrasound cavitation effect.Generally, reaction system cavitation gas is more, is more easy to produce cavitation bubble.One
The adiabatic exponent of reverse side, gas is bigger, and the temperature obtained by cavitation effect is higher, and pressure is bigger, can cause bigger ultrasound
Chemical effect.The adiabatic exponent value of monoatomic gas is greater than the adiabatic exponent value of diatomic and polyatomic gas, and more preferably adopts
With.On the other hand, the degree of sonochemistry effect additionally depends on the heat transfer of gas, and the heat transfer of gas is bigger, more heat
Amount (i.e. cavitation bubble released during collapse heat) is transmitted to the liquid medium of surrounding, so that cavitation temperature drop
Low, chemical effect of ultrasound is weakened.Meanwhile in ultrasonic field, the freedom of the generations such as diatomic cavitation gas such as nitrogen or oxygen
Base can directly participate in degradation reaction.Comprehensively consider adiabatic exponent, pyroconductivity and radical reaction, it is recommended to use argon gas, nitrogen
Gas or oxygen reform the cavitation gas repaired in reaction as cobalt acid lithium supersonic, water-heating.
The power of ultrasonic cavitation effect is related with the physicochemical properties of parameters,acoustic and liquid.Supersonic generator
Power be phonochemical reaction deciding factor.The size of ultrasonic power influences the speed that cavitation bubble is closed and cavitation is strong
Degree, to influence the separation of cobalt acid lithium and reform the effect repaired.Ultrasonic power increases, and ultrasonic energy increases in medium, bears
The stretching action of pressure area is reinforced, and cavitation bubble mushrooms out, and the squeezing action aggravation of zone of positive pressure, cavitation bubble is crumbled and fall rapidly, gas
Motion intense is steeped, the quantity of cavitation point increases therewith, enhances the surge of positive composition material, conducive to the separation of cobalt acid lithium
It is repaired with reforming.But when ultrasonic power is excessive, ultrasonic wave transmitting terminal lower part generates many big holes, and ultrasonic wave is caused to be sent out
It penetrates end to be deteriorated with liquid phase contact condition, sound can be converted into thermal energy to a greater degree, while cavitation bubble is growed in the negative of sound wave
It can not collapse greatly very much, generate a large amount of invalid cavitation bubble, form sound barrier, increase the energy attenuation of ultrasonic wave, it is unfavorable
In the separation and reconstruction reparation of cobalt acid lithium.
The temperature of reaction solution can influence the surface tension and viscosity and vapor pressure liquid of liquid medium, thus shadow
Ring cavitation effect.The temperature of reaction solution is improved in a certain range, and the viscosity of solution reduces, solution medium and cobalt acid lithium particle
It comes into full contact with, is conducive to the reformation reparation of cobalt acid lithium.But the reaction of ultrasonic Separation and reformation cobalt acid lithium should not be in higher temperature
Degree is lower to carry out, and temperature is higher, and solution surface is easy to appear atomizating phenomenon, and bubble in liquid largely increases, and reduces sound intensity utilization rate,
Weaken cavitation effect, is unfavorable for the removal of cobalt acid lithium surface organic matter and the reformation reparation of crystal structure.
The ultrasonication time is an important factor for influencing cobalt acid lithium separation and reform repairing effect.Extend in a certain range
Action time is conducive to the reparation of cobalt acid lithium crystal, this is because cobalt acid lithium obtains more thermal energy in relatively long ultrasonic time
And impact, it is effectively removed PVDF, while being conducive to " dissolution-crystallization " of cobalt acid lithium crystal.When ultrasonic time is too long, cobalt acid
The separation and reformation repairing effect variation of lithium are unobvious, it is contemplated that time cost and Energy Consumption Factors limit cobalt acid lithium in step (1)
Disengaging time be 10-150min, the reformation repair time of cobalt acid lithium is 6-10h in step (3).
Compared with prior art, the invention has the following advantages:
(1) it does not need to carry out break process to useless lithium battery electrode plate, reduces energy consumption；
(2) supersonic, water-heating separates positive and negative electrode technology green high-efficient, does not generate secondary pollution；
(3) this method separates anode and cathode in supersonic, water-heating and carries out supersonic, water-heating structure weight to the cobalt acid lithium after separation
While trimming is multiple, organic binder is realized in cobalt acid lithium surface and gap by solid phase and is transferred to liquid phase, is conducive to its General Office
Reason disposition；
(4) reaction time consumption is short, and substance recovery is high, is suitble to industrial production；
(5) building of reaction system equipment is relatively easy to, and easy to operate, is convenient for industrialization promotion；
(6) while cobalt acid lithium is reformed, graphite, aluminium and the copper in useless electrode of lithium cell component can be recycled.
Present invention process can efficiently separate and recycle cobalt acid lithium, graphite, aluminium and the copper in useless electrode of lithium cell component, together
Lithium in Shi Liyong cathode graphite carries out supersonic, water-heating structure repair to cobalt acid lithium after supersonic, water-heating separation.The present invention can get through negative
In the graphite of pole the recycling of lithium separated with the supersonic, water-heating of positive cobalt acid lithium with reconstruction repair process, realize that elemental lithium is electric in lithium
Recycling in pond.This process is simple, strong operability, without secondary pollution, has good social benefit, economic effect
Benefit and environmental benefit.
Detailed description of the invention
Fig. 1 is the XRD spectrum (10~80 °) that different hydrogen peroxide additive amounts reform cobalt acid lithium after reparation；
Fig. 2 is the XRD spectrum (10~25 °) that different hydrogen peroxide additive amounts reform cobalt acid lithium after reparation；
Fig. 3 is the XRD spectrum (10~80 °) that different argon pressures reform cobalt acid lithium after reparation；
Fig. 4 is the XRD spectrum (18~20 °) that different argon pressures reform cobalt acid lithium after reparation；
Fig. 5 is the XRD spectrum (10~80 °) that supersonic, water-heating separated and reformed cobalt acid lithium after reparation；
Fig. 6 is the XRD spectrum (18~20 °) that supersonic, water-heating separated and reformed cobalt acid lithium after reparation；
Fig. 7 be cobalt acid lithium sample SEM scanning electron microscope (SEM) photograph (a: the cobalt acid lithium of mechanical stripping, b: the cobalt acid lithium of ultrasonic Separation,
C: the cobalt acid lithium that ultrasound is repaired).
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) first used Li ion cell machinery is split, obtains anode and cathode, being shredded into size is 3-5cm2It is broken
Piece.Positive plate 7.5g is placed in 700mL clear water, the hydrogenperoxide steam generator of 1.5mL 30% is added, falls material after mixing
Enter in ultrasonic wave reaction kettle.Control supersonic generator power is 300W, 50 DEG C of heated constant temperature after closed ultrasonic reaction kettle, to super
Phonoresponse kettle applies ultrasonic radiation, while turn on agitator, ultrasonic 60min；When ultrasonic reaction kettle is cooled to room temperature, filtrate
Material obtains cobalt acid lithium lotion and aluminium foil, and is washed 5 times using clear water；The cobalt acid lithium lotion and aluminium foil that filtering is obtained,
Dry 8h, finally obtains cobalt acid lithium and aluminium foil in 80 DEG C of environment.The efficient of cobalt acid lithium and aluminium foil may be implemented in supersonic, water-heating method
Separation reforms the crystal for repairing cobalt acid lithium meanwhile, it is capable to remove the partial organic substances for being adhered to cobalt acid lithium surface to a certain extent
Structure.
(2) negative electrode tab 6g is placed in 200mL clear water, mixed material is poured into ultrasonic response kettle, be heated to 80 DEG C,
Control supersonic generator power is 250W, applies ultrasonic radiation, while turn on agitator, ultrasonic 90min to ultrasonic reaction kettle；
When ultrasonic reaction kettle is cooled to room temperature, filter material obtains graphite lotion and copper foil, and is washed 5 times using clear water；Incited somebody to action
The graphite lotion and copper foil obtained is filtered, dry 8h, finally obtains graphite and copper foil in 80 DEG C of environment；Meanwhile filtrate is collected,
Because lithium-containing compound hydrolyzes in graphite, filtrate made alkaline, pH range about 10.4-10.6 is repaired as cobalt acid lithium reconstruction
Lithium source when multiple.
(3) the about 200mL of the filtrate rich in lithium that the cobalt acid lithium 2g and step (2) for taking step (1) to obtain are obtained, takes 30%
Hydrogenperoxide steam generator 1mL pours into material in ultrasonic response kettle after mixing, is heated to 80 DEG C, is passed through argon gas 0.4MPa, applies
The Ultrasonic Radiation 6h of 850W；When ultrasonic reaction kettle is cooled to room temperature, filter material obtains the cobalt acid lithium of reconstruction reparation
Lotion, and washed 5 times using clear water；The cobalt acid lithium lotion that filtering is obtained dry 8h in 80 DEG C of environment.
In addition, separating cobalt acid lithium and aluminium foil using the method for mechanical stripping, cobalt acid lithium is taken to carry out XRD test, SEM
Test and electrical performance testing；Only by step (1) supersonic, water-heating method, cobalt acid lithium is separated with aluminium foil, cobalt acid lithium is taken to carry out XRD
Test, SEM test and electrical performance testing.By step (3) supersonic, water-heating reform repairing method, take cobalt acid lithium carry out XRD test,
SEM test and electrical performance testing.
Fig. 5 is supersonic, water-heating separation and the XRD spectrum (10~80 °) for reforming cobalt acid lithium after reparation.Fig. 6 is supersonic, water-heating point
From and reform repair after cobalt acid lithium XRD spectrum (18~20 °).Table 1 is metal ion content and lithium cobalt ratio in cobalt acid lithium.Figure
7 be the SEM scanning electron microscope (SEM) photograph of cobalt acid lithium, compared the cobalt acid lithium of mechanical stripping, the cobalt acid lithium of supersonic, water-heating separation and ultrasonic water
The pattern of the cobalt acid lithium of thermal reforming reparation.
By Fig. 5 and Fig. 6 as it can be seen that compared to mechanical stripping cobalt acid lithium, supersonic, water-heating separation after cobalt acid lithium XRD curve more
Add smooth, miscellaneous peak is reduced, and (003) diffraction maximum is gradually from bimodal to unimodal transformation, at (018)/(110) and (006)/(102)
Diffraction maximum is drifted apart from.The testing result such as table of cobalt lithium content and lithium cobalt ratio in cobalt acid lithium after mechanical stripping and supersonic, water-heating separation
1, lithium cobalt ratio increases to 0.8735 by 0.7717, because of remaining electrolyte LiPF in failure cobalt acid lithium6Liquid phase is entered, ultrasound
The mechanical effect and cavitation effect of wave promote lithium ion to be entered in cobalt acid lithium layer structure by liquid phase.It is compared by Fig. 7 (a) and (b)
As it can be seen that the layer structure of cobalt acid lithium has obtained a degree of heavy after supersonic, water-heating separation compared with the cobalt acid lithium of mechanical stripping
Trimming is multiple, and interlayer faults collapse phenomenon is mitigated, and shows supersonic, water-heating method while separating cobalt acid lithium and aluminium foil, one
Determine the layer structure that cobalt acid lithium has been reformed in degree.
By Fig. 5 and Fig. 6 as it can be seen that compared to ultrasonic Separation failure cobalt acid lithium, supersonic, water-heating is reformed repair after cobalt acid lithium
Diffraction maximum becomes apparent from, and peak type is more sharp, and (003) diffraction maximum is moved to right to 19.2 °, spreads out at (018)/(110) and (006)/(102)
It is completely separable to penetrate peak.As shown in table 1, the lithium cobalt ratio in the cobalt acid lithium of ultrasonic Separation is 0.8735, and lithium cobalt ratio increases to after reformation
1.011.It is compared by Fig. 7 (b) and (c) as it can be seen that cobalt acid lithium surface organic matter is obviously removed, layer structure is obviously restored, brilliant
Lithium content increases in body, shows using the lithium in cathode graphite as additional lithium source, and the mechanical effect and cavitation effect of ultrasonic wave promote
Solid phase is entered by liquid phase into lithium ion, increases lithium content in cobalt acid lithium layer structure, reforms the stratiform for having repaired cobalt acid lithium
Structure.
Repairing method is reformed by step (3) supersonic, water-heating, different hydrogen peroxide (remaining condition is constant) additive amounts is taken to reform
Cobalt acid lithium after reparation carries out XRD test.Fig. 1 is the XRD spectrum (10 that different hydrogen peroxide additive amounts reform cobalt acid lithium after reparation
~80 °).Fig. 2 is supersonic, water-heating separation and the XRD spectrum (10~25 °) for reforming cobalt acid lithium after reparation.Fig. 1 and Fig. 2 were reflected
Hydrogen oxide additive amount reforms the influence of repairing effect to cobalt acid lithium.
By Fig. 1 and Fig. 2 as it can be seen that when not adding hydrogen peroxide, the XRD spectrum of cobalt acid lithium there are some miscellaneous peaks, 003,
101,104 diffraction maximums are shown the characteristics of characteristic feature peak, and 003 peak is moved to right to 18.9 °, (006)/(012) and (018)/(110)
It is drifted apart from, the crystal structure of cobalt acid lithium is restored.It improves hydrogen peroxide additive amount (1-4mL), miscellaneous peak disappears, curve relatively light
Sliding, 003 diffraction maximum is moved to right to 18.9 ° -19.0 °, and peak type is sharp, and (006)/(012) and (018)/(110) are completely separable, cobalt
Sour crystalline lithium has good crystal form, this is because hydrogen peroxide is added, the free radicals such as OH increase under ultrasonication, high oxidation
The concentration of free love base increases, and free radical is increase accordingly with organic matter contact probability on cobalt acid lithium particle in unit volume, effectively
Remove the PVDF on cobalt acid lithium surface.But when excessive hydrogen peroxide is added, part OH free radical can and OH, H and
H2It is quenched etc. reacting, the oxidability of liquid phase reduces instead, is unfavorable for the reformation reparation of cobalt acid lithium.
Different argon gas in step (3) are taken to be passed through the cobalt acid lithium progress XRD survey after pressure (remaining condition is constant) reformation is repaired
Examination.Fig. 3 is the XRD spectrum (10~80 °) that different argon pressures reform cobalt acid lithium after reparation.Fig. 4 is that different argon pressures are reformed
The XRD spectrum (18~20 °) of cobalt acid lithium after reparation.Fig. 3 and Fig. 4 reflects argon gas and is passed through the shadow for reforming repairing effect to cobalt acid lithium
It rings.The argon gas for being passed through 0-0.5MPa pressure promotes the supersonic, water-heating reformation reparation of cobalt acid lithium.By Fig. 3 and Fig. 4 as it can be seen that being passed through argon
When the pressure of gas is 0-0.5MPa, the XRD curve of cobalt acid lithium becomes smooth, and 003 diffraction maximum is moved to right to 19.2 °, (018)/(110)
And (006)/(102) are completely separable, peak type is sharp, shows that the layer structure of cobalt acid lithium is restored, crystallinity is preferable.With more
Argon gas dissolution in the solution, conducive to the generation of cavitation bubble, cavitation effect enhancing, the temperature and pressure obtained by cavitation bubble collapse
Power improves, and is conducive to the removal degradation and the reformation reparation of cobalt acid lithium of PVDF.But when the too high levels of cavitation gas, such as
Shown in Fig. 3 and Fig. 4, when being passed through the pressure of argon gas greater than 0.5MPa, the cavitation gas molecule quantity in solution is excessive, increases
The buffering effect of cavitation gas is unfavorable for the collapse of cavitation bubble, the intensity of shock wave when reducing cavitation bubble collapse.In addition, molten
Liquid cavitation gas content is excessively high, and the energy for being unfavorable for cavitation bubble collapse acts on cobalt acid lithium, the dissipation of a large amount of ultrasonic wave heats
Can also solution temperature be made to increase, reduce the surface tension of reaction medium, weakened temperature and pressure when cavitation bubble collapse, be unfavorable for
The removal of organic matter and the reformation reparation of cobalt acid lithium.
Button cell is prepared with the cobalt acid lithium that ultrasound is reformed after repairing, and examines its chemical property.Button cell fills
Discharge test the result shows that: supersonic, water-heating reform repair after cobalt acid lithium material discharge capacity for the first time reach 129.0mAh/g, 50 times
Charge and discharge cycles capacity is reduced to 97.3%.
Table 1
Embodiment 2
(1) first used Li ion cell machinery is split, obtains anode and cathode, being shredded into size is 3-5cm2It is broken
Piece.Positive plate 5g is placed in 700mL clear water, 30% hydrogenperoxide steam generator 2mL is added, material is poured into ultrasound after mixing
In wave reaction kettle.Control supersonic generator power is 250W, 75 DEG C of heated constant temperature after closed ultrasonic reaction kettle, to ultrasonic reaction
Kettle applies ultrasonic radiation, while turn on agitator, ultrasonic 45min；When ultrasonic reaction kettle is cooled to room temperature, filter material is obtained
Cobalt acid lithium lotion and aluminium foil, and washed 5 times using clear water；The cobalt acid lithium lotion and aluminium foil that filtering is obtained, in 80 DEG C of rings
Dry 8h, finally obtains cobalt acid lithium and aluminium foil in border；
(2) negative electrode tab 8g is placed in 200mL clear water, mixed material is poured into ultrasonic response kettle, be heated to 90 DEG C,
Control supersonic generator power is 200W, applies ultrasonic radiation, while turn on agitator, ultrasonic 80min to ultrasonic reaction kettle；
When ultrasonic reaction kettle is cooled to room temperature, filter material obtains graphite lotion and copper foil, and is washed 5 times using clear water；Incited somebody to action
The graphite lotion and copper foil obtained is filtered, dry 8h, finally obtains graphite and copper foil in 80 DEG C of environment；Meanwhile collecting filtrate.
(3) the about 200mL of the filtrate rich in lithium that the cobalt acid lithium 2g and step (2) for taking step (1) to obtain are obtained, takes 30%
Hydrogenperoxide steam generator 1.5mL pours into material in ultrasonic response kettle after mixing, is heated to 90 DEG C, is passed through argon gas 0.5MPa, applies
Add the Ultrasonic Radiation 6h of 750W；When ultrasonic reaction kettle is cooled to room temperature, filter material obtains cobalt acid lithium lotion, and using clear
Water washing 5 times；The cobalt acid lithium lotion that filtering is obtained dry 8h in 80 DEG C of environment, after finally obtaining supersonic, water-heating reformation reparation
Positive electrode active materials cobalt acid lithium；
The charge-discharge test of button cell the result shows that: supersonic, water-heating is reformed repair after the electric discharge for the first time of cobalt acid lithium material hold
Amount reaches 128.2mAh/g, and 50 times charge and discharge cycles capacity is reduced to 96.8%.
Embodiment 3
(1) first used Li ion cell machinery is split, obtains anode and cathode, being shredded into size is 3-5cm2It is broken
Piece.Positive fragment 7.5g is placed in 700mL clear water, the hydrogenperoxide steam generator of 2.5mL 30% is added, by material after mixing
It pours into ultrasonic response kettle.Control supersonic generator power is 350W, right 60 DEG C of heated constant temperature after closed ultrasonic reaction kettle
Ultrasonic reaction kettle applies ultrasonic radiation, while turn on agitator, ultrasonic 30min；When ultrasonic reaction kettle is cooled to room temperature, filtering
Material obtains cobalt acid lithium lotion and aluminium foil, and is washed 5 times using clear water；The cobalt acid lithium lotion and aluminium foil that filtering is obtained,
Dry 8h, finally obtains cobalt acid lithium and aluminium foil in 80 DEG C of environment；
(2) negative electrode tab 10g is placed in 200mL clear water, is poured into ultrasonic response kettle, be heated to 90 DEG C, control ultrasound
Wave producer power is 200W, applies ultrasonic radiation, while turn on agitator, ultrasonic 75min to ultrasonic reaction kettle；To ultrasonic anti-
When kettle being answered to be cooled to room temperature, filter material obtains graphite lotion and copper foil, and is washed 5 times using clear water；Filtering is obtained
Graphite lotion and copper foil, dry 8h, obtains graphite and copper foil in 80 DEG C of environment；Meanwhile collecting filtrate.
(3) the about 200mL of the filtrate rich in lithium that the cobalt acid lithium 2g and step (2) for taking step (1) to obtain are obtained, takes 30%
Hydrogenperoxide steam generator 1.5mL pours into material in supersonic, water-heating reaction kettle after mixing, is heated to 80 DEG C, is passed through argon gas
0.45MPa applies the Ultrasonic Radiation 6h of 1000W；When ultrasonic reaction kettle is cooled to room temperature, filter material obtains cobalt acid lithium cream
Body, and washed 5 times using clear water；The cobalt acid lithium lotion that filtering is obtained dry 8h in 80 DEG C of environment, obtains supersonic, water-heating weight
Cobalt acid lithium after trimming is multiple.
Embodiment 4
(1) first used Li ion cell machinery is split, obtains anode and cathode, being shredded into size is 3-5cm2It is broken
Piece.Positive fragment 30g is placed in 700mL clear water, the hydrogenperoxide steam generator of 6mL 30% is added, pours into material after mixing
In ultrasonic response kettle.Control supersonic generator power is 500W, 40 DEG C of heated constant temperature after closed ultrasonic reaction kettle, to ultrasound
Reaction kettle applies ultrasonic radiation, while turn on agitator, ultrasonic 150min；When ultrasonic reaction kettle is cooled to room temperature, filtrate
Material obtains cobalt acid lithium lotion and aluminium foil, and is washed 4 times using clear water；The cobalt acid lithium lotion and aluminium foil that filtering is obtained,
Dry 10h, finally obtains cobalt acid lithium and aluminium foil in 60 DEG C of environment；
(2) negative electrode tab 10g is placed in 200mL clear water, is poured into ultrasonic response kettle, be heated to 75 DEG C, control ultrasound
Wave producer power is 90W, applies ultrasonic radiation, while turn on agitator, ultrasonic 120min to ultrasonic reaction kettle；To ultrasonic anti-
When kettle being answered to be cooled to room temperature, filter material obtains graphite lotion and copper foil, and is washed 4 times using clear water；Filtering is obtained
Graphite lotion and copper foil, dry 10h, obtains graphite and copper foil in 60 DEG C of environment；Meanwhile collecting filtrate.
(3) the about 200mL of the filtrate rich in lithium that the cobalt acid lithium 5g and step (2) for taking step (1) to obtain are obtained, will after mixing
Material pours into supersonic, water-heating reaction kettle, is heated to 100 DEG C, is passed through argon gas 0.2MPa, applies the Ultrasonic Radiation 8h of 1150W；
When ultrasonic reaction kettle is cooled to room temperature, filter material obtains cobalt acid lithium lotion, and is washed 4 times using clear water；Filtering is obtained
Cobalt acid lithium lotion in 60 DEG C of environment dry 10h, obtain supersonic, water-heating and reform the cobalt acid lithium after repairing.
Embodiment 5
(1) first used Li ion cell machinery is split, obtains anode and cathode, being shredded into size is 3-5cm2It is broken
Piece.Positive fragment 20g is placed in 700mL clear water, is poured into material in ultrasonic response kettle after mixing.Control ultrasonic wave hair
Device power is given birth to as 90W, 25 DEG C of heated constant temperature after closed ultrasonic reaction kettle, ultrasonic radiation is applied to ultrasonic reaction kettle, is opened simultaneously
Blender, ultrasonic 10min；When ultrasonic reaction kettle is cooled to room temperature, filter material obtains cobalt acid lithium lotion and aluminium foil, and makes
It is washed 3 times with clear water；The cobalt acid lithium lotion and aluminium foil that filtering is obtained, the dry 9h in 70 DEG C of environment, finally obtain cobalt acid
Lithium and aluminium foil；
(2) negative electrode tab 8g is placed in 200mL clear water, is poured into ultrasonic response kettle, be heated to 75 DEG C, control ultrasonic wave
Generator power is 500W, applies ultrasonic radiation, while turn on agitator, ultrasonic 60min to ultrasonic reaction kettle；To ultrasonic reaction
When kettle is cooled to room temperature, filter material obtains graphite lotion and copper foil, and is washed 3 times using clear water；The stone that filtering is obtained
Black lotion and copper foil, dry 9h, obtains graphite and copper foil in 70 DEG C of environment；Meanwhile collecting filtrate.
(3) the about 200mL of the filtrate rich in lithium that the cobalt acid lithium 4g and step (2) for taking step (1) to obtain are obtained is added 30%
Hydrogen peroxide 4mL, material is poured into supersonic, water-heating reaction kettle after mixing, is heated to 70 DEG C, is passed through nitrogen 0.1MPa, apply
The Ultrasonic Radiation 10h of 800W；When ultrasonic reaction kettle is cooled to room temperature, filter material obtains cobalt acid lithium lotion, and using clear
Water washing 3 times；The cobalt acid lithium lotion that filtering is obtained dry 9h in 70 DEG C of environment obtains supersonic, water-heating and reforms the cobalt after repairing
Sour lithium.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation, which comprises the following steps:
(1) positive plate of lithium battery is placed in clear water, 30% hydrogenperoxide steam generator, ultrasonic reaction is added, cooling, filtering is washed
It washs, dry, obtain the cobalt acid lithium of poor lithium；
(2) lithium battery cathode plate is placed in clear water, ultrasonic reaction is carried out after mixing, cooling is filtered, washed, and is collected and is rich in lithium
Filtrate；
(3) filtrate rich in lithium for obtaining the cobalt acid lithium for the poor lithium that step (1) obtains, step (2) with 30% hydrogen peroxide
Solution mixing, pours into ultrasonic response kettle, is passed through cavitation gas and removes air and enhance cavitation effect, carries out ultrasonic reaction, cold
But, be filtered, washed, dry after obtain the cobalt acid lithium of reconstruction reparation.
2. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, in step (1): solid-to-liquid ratio 1:140-3:70g/mL, mixeding liquid volume are the 60-70% of reactor volume.
3. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, in step (1): the volume ratio of the hydrogenperoxide steam generator of addition and clear water is 1:1400-1:100.
4. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, the process conditions of ultrasonic reaction in step (1) are as follows: mixing speed 30-200r/min, reaction temperature are 25-75 DEG C, are surpassed
Sonic generator power is 90-500W, reaction time 10-150min.
5. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, in step (2): solid-to-liquid ratio 3:100-1:20g/mL, mixeding liquid volume are the 60-70% of reactor volume.
6. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, the process conditions of ultrasonic reaction in step (2) are as follows: mixing speed 30-200r/min, reaction temperature are 75-90 DEG C, are surpassed
Sonic generator power is 90-500W, reaction time 60-120min.
7. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, in step (3): the volume ratio that hydrogenperoxide steam generator and clear water is added is 1:400-1:50.
8. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, in step (3): solid-to-liquid ratio is 1:100~1:40g/mL, and mixeding liquid volume is the 60-70% of reactor volume.
9. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, the process conditions of ultrasonic reaction in step (3) are as follows: the pressure of cavitation gas is 0-0.5MPa, reaction temperature 70-100
DEG C, supersonic generator power is 750-1150W, reaction time 6-10h.
10. the method for a kind of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation according to claim 1, feature
It is, the washing is washed 3-5 times using clear water, and the drying temperature is 60-80 DEG C, drying time 8-10h.
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