CN106654439A - Utilization method of waste lithium ion battery anode carbon material - Google Patents
Utilization method of waste lithium ion battery anode carbon material Download PDFInfo
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- CN106654439A CN106654439A CN201710101487.6A CN201710101487A CN106654439A CN 106654439 A CN106654439 A CN 106654439A CN 201710101487 A CN201710101487 A CN 201710101487A CN 106654439 A CN106654439 A CN 106654439A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a utilization method of a waste lithium ion battery anode carbon material. The method comprises the step of compounding a recycled carbon material separated from a waste lithium ion battery with sulfur to prepare a lithium-sulfur battery cathode material; and the specific steps are as follows: discharging the waste lithium ion battery, disassembling, making adhesive failure and peeling in the water, removing impurities of ferric iron source, activating, and compounding with elemental sulfur, and finally manufacturing the carbon sulfur compound anode material for a lithium sulfur battery. A recycling scheme of taking recycled carbon material of the waste lithium ion battery as the raw material to prepare the high-performance lithium-sulfur battery compound anode material realizes the high-economic additional value recycling of the waste lithium ion battery negative electrode carbon material, is high in recycling efficiency, clean and environment-friendly; the prepared carbon sulfur compound anode material is strong in sulfur absorbing capacity, and excellent in rate performance and cycle performance.
Description
Technical field
The present invention relates to the carbon material used as anode recovery technology field in waste and old lithium ion battery, and in particular to one kind is utilized back
The method that the waste and old lithium ion battery carbon material used as anode of receipts prepares composite anode material for lithium sulfur battery.
Background technology
Lithium ion battery has the shortcomings that high voltage, high-energy-density, long circulation life due to it, from the nineties in last century with
To have obtained more and more widely using in mankind's daily life.From 3C Product field originally at present electric automobile,
The extensive application of electrical network energy storage etc..With the large-scale application of lithium ion battery, China has become maximum in the world at present
Battery production state, 1～October in 2016, China's lithium ion battery cumulative production was up to 606112.3 ten thousand, it is contemplated that the coming five years
(2017～2021) annual average compound growth rate will be up to 7.17%.China's electrokinetic cell in 2015 adds up learies and is about 1000
Ton, it was predicted that to before and after the year two thousand twenty, the various power Vehicular battery learies of China will be more than 10,000 tons.Contain in lithium ion battery
Element and the organic electrolytes such as a large amount of copper, cobalt, nickel, not carrying out processing after scrapping will necessarily cause serious environmental pollution, destroy
Ecological environment.But there is the elements such as the lithium, cobalt, nickel, the copper that are wherein rich in very big recycling to be worth, therefore, waste and old lithium from
The recycling of sub- battery and production waste material has become countries in the world urgent need to solve the problem.
At present, the recovery and reuse technology of waste and old lithium ion battery is concentrated mainly on to metals such as lithium, copper, cobalt, nickel
In recycling, and the recycling method for being directed to battery negative pole carbon material is then relatively fewer.Some recovery technologies will be reclaimed
The Carbon anode for arriving, regains negative electrode for lithium ion battery slurry by the way of feed supplement.But in the preparation of lithium ion battery
During, the battery material for being used is strict to index requests such as constituent content, impurity concentration, granularities, reclaims the carbon materials for obtaining
Material is containing graphite, conductive carbon black and containing lithium solid electrolyte and is difficult to remove on a small quantity, therefore, the negative pole material obtained using this method
Material is difficult to meet the requirement as lithium ion battery negative material, again will greatly shadow as ion cathode material lithium using it
The chemical property of lithium ion battery is rung.
At present, most of recovery and utilization technology all only resides within the aspect of recovery, and the material with carbon element to reclaim does not find
Land use systems with high economic value added, lithium ion battery negative pole carbon material is for the graphite of high-quality and with good electric conductivity
Acetylene black, conductive carbon black etc., the high value for being difficult to waste as Land use systems such as lubricating graphites utilizes.
Lithium-sulfur cell is the high-energy density secondary battery of great development potentiality and application prospect, and it has height ratio capacity
(1675mAh/g) with high-energy-density (2600Wh/kg).Its positive electrode is mainly carbon sulphur composite, and negative material is gold
Category lithium.Stability Analysis of Structures, electric conductivity are good, the big carbon sulphur composite for carrying sulfur content is that lithium-sulfur cell possesses excellent high rate performance and height
The key of specific capacity.Elemental sulfur adsorbs on porous material skeleton, and the polysulfide in long-time cyclic process can dissolve
Spread in electrolyte and by electrolyte, that is, shuttle effect is produced, the problems such as cause serious self discharge and capacity attenuation.Mesh
Before, in order to reduce shuttle effect as far as possible, the sandwich that lithium sulfur battery anode material needs design complicated is carried out to polysulfide
Physical absorption is needed material disperses such as the oxides with chemical sulfur fixation using complicated preparation method in carbon bone
On frame, and it is difficult to keep being uniformly dispersed for adsorbent.
In prior art, waste and old lithium ion battery carbon material used as anode needs a kind of recycling with high economic value added badly
Technology.In addition, the carbon sulphur composite of existing lithium-sulfur cell needs one kind badly and prepares simple preparation method.
The content of the invention
The present invention is relatively fewer for the recycling method of existing waste and old lithium ion battery carbon material used as anode, recovery
The problems such as material with carbon element lacks the Land use systems with high economic value added, the invention provides a kind of waste and old lithium ion battery negative pole
The Application way of material with carbon element, it is intended to which the high price for realizing lithium ion battery negative pole carbon material is reclaimed.
A kind of Application way of waste and old lithium ion battery carbon material used as anode, will be isolated again from waste and old lithium ion battery
Raw material with carbon element is combined with sulphur, and lithium-sulfur cell carbon sulphur composite positive pole is obtained.
The inventors discovered that, carbon raw material is used as using the material for reclaiming from waste and old lithium ion battery carbon material used as anode, regenerating,
It is compound with sulphur simple substance, the carbon with good electrical performance/sulphur composite can be obtained, the carbon/sulphur composite is used as lithium sulphur electricity
Dissolving of the positive electrode in pond to polysulfide has good inhibitory action, can show good electric property；For example, energy
It is obviously improved the cycle performance of lithium-sulfur cell.
In the present invention, by the regeneration material with carbon element reclaimed from lithium ion battery and sulphur simple substance by being simply combined (mixing) i.e.
The lithium sulfur battery anode material with good electrical performance can be obtained, preparation method is simple, and realizes the material of lithium battery
High economic value added utilize.
In the present invention, retain the film containing lithium solid electrolyte in waste and old lithium ion battery carbon material used as anode；Improve regenerative carbon
The sulphur performance of receiving of material has considerable influence to the performance of obtained lithium sulfur battery anode material.
By further investigation, the present inventor explores the Application way of following waste and old lithium ion battery carbon material used as anode：Will
Waste and old lithium ion battery is discharged successively, is disassembled, failure stripping binding agent reclaims the carbon raw material that must give up in water, and useless carbon raw material is again
Jing ferric iron source removal of impurities, activation and elemental sulfur are combined, the composite positive pole of final prepared lithium-sulfur cell carbon sulphur.
Application way of the present invention, specifically includes following steps：
Step (1)：Discharge, disassemble, separating and to obtain cathode pole piece by waste and old lithium ion battery, by the cathode pole piece cutting for obtaining
After impregnated in water, ultrasound and/or stirring under peel off；Subsequently sieve, separate to obtain Copper Foil and material with carbon element suspension；
Step (2)：Ferric iron source is added in material with carbon element suspension, subsequently Jing separation of solid and liquid, washing, dry, broken successively
It is broken, sieving obtains material with carbon element；
Step (3)：Be incorporated in protective atmosphere under mixed with activator of the material with carbon element that step (2) is obtained activates；Activation
Product is scrubbed, dry, crush, sieving must regenerate material with carbon element；
Step (4)：The regeneration material with carbon element that step (3) is obtained carries out ball milling mixing with elemental sulfur, lithium-sulfur cell is obtained and uses
Carbon sulphur composite positive pole.
In the present invention, described negative pole pole is peeled off under acid-free condition, with after Jing ferric iron sources process be obtained carbon materials
Material, described material with carbon element and activator are activated, and can be obtained with well receiving sulphur performance, the regenerative carbon containing lithium solid electrolyte film
Material；Originally obtained regeneration material with carbon element is combined with sulphur again the positive electrode as lithium-sulfur cell is obtained.It is obtained
Positive electrode can slow down the shuttle effect of polysulfide in the lithium-sulfur cell course of work, improve the cycle performance of lithium-sulfur cell.
In step (1), waste lithium iron phosphate battery is substantially discharged, described being substantially discharged preferably be discharged to termination electricity
Force down in 1V.
In step (1), it is substantially discharged for example in salt discharge in water；Described salt solution is, for example, sodium-chloride water solution.
Waste lithium iron phosphate battery after being substantially discharged is disassembled, cathode pole piece is separated to obtain；Subsequently by the negative pole pole for obtaining
Into the fragment of silk ribbon shape after piece cutting.
Cathode pole piece after cutting is placed in water, under ultrasound and stirring adhesive failure is peeled off.In the present invention, phase
The binding agent for being compared to acid or alkali peels off mode, the carbon material used as anode for obtaining is peeled off in water and more conducively lifts lithium-sulphur cell positive electrode
The electric property of material.
In step (1), the frequency of ultrasound is 30～60kHz；The rotating speed of stirring is 100～500r/min.
In step (1), stirring under the parameter and under the synergy of ultrasound, make negative material completely, peel off, it is real
The quick separating of existing negative material and collector.
In step (1), ultrasound and stirring in water, on Copper Foil till basic noresidue.
In step (1), after negative material is separated with collector, sieving separating obtains Copper Foil and material with carbon element suspension.
In the present invention, by the process of ferric iron source, the Cu during battery recycling can be removed2+Deng impurity；Avoid closing
Into carbon/sulphur positive electrode contain undesired impurities, and then avoid lithium-sulfur cell self discharge.
Preferably, described ferric iron source is water-soluble trivalent ferric salt；For example, the chloride of three-level iron, nitrate,
Sulfate etc..
Further preferably, the ferric iron source is at least one in iron chloride, ferric nitrate, ferric sulfate.
In step (2), ferric iron source is added in material with carbon element suspension, Fe in system3+Concentration be preferably 0.1～
5mol/L, more preferably 2mol/L.
In step (2), the system after ferric iron source is processed carries out separation of solid and liquid, and collection obtains solid for the carbon after removal of impurities
Material；Material with carbon element after the removal of impurities is washed.
In step (2), the solvent that washing process is adopted is for alcohol solution.
The inventors discovered that, can effectively be removed using alcohol solution washing and reclaim the organic adhesive remained in material with carbon element
Agent, and the stable existence of solid electrolyte film can be kept.
Preferably, in described alcohol solution, the volumetric concentration of alcohol is 5%～50%；More preferably 10%～
20%.
Described alcohol is can be with water infinitely than miscible small molecular alcohol.
Preferably, unit or or polyalcohol of the described alcohol for C2～4.
Further preferably, described alcohol is ethanol, isopropanol etc..
Still more preferably, described alcohol is ethanol.
Preferably, in step (2), the solvent that washing process is adopted is for ethanol water；In described ethanol water,
The volumetric concentration of ethanol is 5%～50%；More preferably 10%～20%.
Described in alcohol solution washing after solid drying, crush, sieving obtains material with carbon element；Preferably, described
Material with carbon element particle diameter be 100～300 mesh；More preferably 150 mesh.
Preferably, in step (3), the weight ratio of activator and material with carbon element is 1～10: 1.
Further preferably, the weight ratio of activator and material with carbon element is 5～8: 1.
Preferably, the hybrid mode of activator and material with carbon element is ball milling.
Further preferably, in step (3), the rotating speed of ball milling is 300～800r/min；Ratio of grinding media to material is 1～6: 1.
Still more preferably, in step (3), the rotating speed of ball milling is 600r/min；Ratio of grinding media to material is 6: 1.
Preferably, described activator is alkali metal hydroxide and/or salt.
Further preferably, described activator for sodium hydroxide, sodium salt, the hydroxide of potassium, sylvite at least
It is a kind of.
Still more preferably, described activator is potassium hydroxide.
Preferably, activation process is carried out under protective atmosphere.
Described protective atmosphere is preferably nitrogen and/or inert gas.
Described inert gas is, for example, helium, argon gas etc..
Preferably, in step (3), activation temperature is 800～900 DEG C, soak time is the time to be 0.5～3.0h.
Further preferably, under described activation temperature, it is 0.5～1.5h the times that soak time is.
Preferably, in step (3), activator and material with carbon element are mixed by weight the ratio for 1～10: 1 be incorporated in it is lazy
Property atmosphere, 0.5～1.5h is activated at 800～900 DEG C.
Under the collaboration of the preferred mass ratio, activation temperature and soak time, can be obtained as follow-up immobilized elemental sulfur
Abundant duct is provided, the regeneration material with carbon element for carrying sulfur content is improved, the activation process described in Jing contributes to further slowing down lithium sulphur electricity
The shuttle effect of polysulfide, improves the cycle performance of lithium-sulfur cell in the course of work of pond.
In step (3), the material after activation is rinsed with water, be broken into powder after filtration, vacuum drying, sieve and must regenerate
Material with carbon element.
Preferably, the particle diameter of described regeneration material with carbon element is 100～300 mesh；More preferably 150 mesh.
The obtained regeneration material with carbon element of step (3) is mixed with elemental sulfur；Preferably, in step (4), regeneration material with carbon element with
The mass ratio of sulphur simple substance is 1: 0.1～1.1.
Further preferably, it is 1: 0.6～1 to regenerate material with carbon element with the mass ratio of sulphur simple substance.
Preferably, the hybrid mode of step (4) is ball milling, the rotating speed of ball milling is 300～800r/min；Ratio of grinding media to material is 1
～6: 1.
Still more preferably, in step (4), the rotating speed of ball milling is 600r/min；Ratio of grinding media to material is 6: 1.
In step (4), Ball-milling Time is preferably 4～8h.
A kind of recycling method of waste and old lithium ion battery carbon material used as anode of the present invention, comprises the following steps：
Step (a)：Waste and old lithium ion battery is discharged, is disassembled, pole piece is cut into silk by isolated cathode pole piece
The fragment of banding；
Step (b)：Silk ribbon chips are placed in pure water and stir after ultrasound 6h, due to adhesive failure material with carbon element and Copper Foil point
From by the removing Copper Foil that sieves, the solution of the carbon material powder for obtaining adds trivalent iron salt to be sufficiently stirred for 3h, the carbon being filtrated to get
Material is rinsed and filtered with the certain volume concentration ethanol aqueous solution again, and filter cake is broken into powder, mistake after being vacuum dried at 100 DEG C
Sieve；The volumetric concentration of ethanol is 5%～50% in ethanol water；Described trivalent iron salt is ferric sulfate；
Step (c)：Weighing the carbon material powder after sieving adds a certain amount of potassium hydroxide or sodium chloride to carry out high energy ball
Mill 3h, mixed-powder is placed in inert atmosphere and activates 0.5h at 800 DEG C, reuses pure water rinsing, is vacuum dried after filtration and breaks
Powder is broken into, sieving must regenerate material with carbon element；Wherein, the quality that adds of potassium hydroxide or sodium chloride is 1 with the mass ratio of material with carbon element
～10: 1；The rotating speed of the high-energy ball milling is 300～800r/min, and ratio of grinding media to material is (1～6): 1；
Step (d)：It is in mass ratio 1: 0.8～1 material with carbon element for preparing step (c) and elemental sulfur mixing, high-energy ball milling
After 6h, you can high-performance lithium sulphur battery carbon sulphur composite positive pole is obtained；The rotating speed of the high-energy ball milling is 300～800r/
Min, ratio of grinding media to material is (1～6): 1；.
The carbon sulphur composite of the present invention prepares lithium-sulfur cell and its performance is carried out as lithium sulfur battery anode material
The method of test：Weigh the carbon sulphur composite of said method preparation, 5wt.%PVDF as binding agent, it is ground fully after
Add a small amount of NMP to be mixed to form uniform black paste slurry, these slurries are coated in aluminum foil current collector as test electricity
Pole, with metal lithium sheet, as a comparison electrode assembling becomes button cell, its adopt electrolyte system for LTFSI/DOL: DME (1:
1).Charging and discharging currents density used by test loop performance is 1000mA g-1(1C multiplying powers).
Beneficial effect：
1st, waste and old lithium ion battery carbon material used as anode is originally applied to the positive electrode of lithium-sulfur cell by the present invention
Preparation field, by simple complex method the lithium sulfur battery anode material with good electrical performance is can be prepared by.In addition, this
Invention is again in conjunction with waste and old lithium ion battery carbon material used as anode without Ore Leaching, Fe3+Removal of impurities, the cleaning of alcohol aqueous solvent, activation work
Skill and the operation such as compound, the regulation and control of parameter with sulphur, can further lift the electrical property of obtained lithium sulfur battery anode material
Energy.
2nd, it is what is reclaimed instant invention overcomes the recycling of waste and old lithium ion battery carbon material used as anode is worth low shortcoming
High-quality material with carbon element provides the Land use systems of high economic value added, and technical scheme is simple.Battery material is typically active
Material, conductive agent, binding agent, thickener etc. are constituted, and by recoverying and utilizing method of the present invention, can take full advantage of recovery
Carbon negative pole material in containing high-quality graphite and the characteristics of conductive agent, be prepared into after lithium sulfur battery anode material without the need for add again
Conductive agent, by need to only adding appropriate thickener and binding agent positive pole plate of lithium-sulfur cell is prepared into, and improves the profit of material
With rate, cost is reduced.
3rd, exist containing lithium solid electrolyte in the material with carbon element for also using recovery of the invention, lithium-sulfur cell can be suppressed to be circulated throughout
The dissolving of polysulfide in journey, improves the cycle performance of lithium-sulfur cell.Therefore, height can be prepared using the carbon material used as anode for reclaiming
The lithium-sulfur cell carbon sulphur composite positive pole of performance.
Description of the drawings
【Fig. 1】It is the charge and discharge electrical schematic of lithium-sulfur cell carbon sulphur composite positive pole prepared by embodiment 1.
【Fig. 2】It is that embodiment 1 is right with the circulation of the discharge capacity of lithium-sulfur cell carbon sulphur composite positive pole prepared by comparative example 1
Than figure.
Specific embodiment
Following examples are intended to be described in further details present invention, and the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
Step (1)：100kg waste and old lithium ion batteries are discharged, disassembled, isolated cathode pole piece is cut out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2)：Silk ribbon chips are placed in 1000L pure water and stir after ultrasound 6h, due to adhesive failure material with carbon element and
Copper Foil is separated, and by the removing Copper Foil that sieves, the solution of the carbon material powder for obtaining adds the ferric sulfate of 2000mol to be sufficiently stirred for
3h, the material with carbon element being filtrated to get is rinsed three times and filtered, filter cake vacuum at 100 DEG C with 15% volumetric concentration ethanol water again
Powder is broken into after drying, 150 mesh sieves is crossed and is obtained carbon material powder；
Step (3)：Weighing the carbon material powder after 0.5kg sieves adds 3kg potassium hydroxide high under 600r/min rotating speeds
Can ball milling 3h (ratios of grinding media to material：6: 1), mixed-powder is placed in argon gas atmosphere and activates 0.5h at 800 DEG C, reuse pure water rinsing three
Time, it is vacuum dried at 100 DEG C after filtration, powder is broken into, crossing 150 mesh sieves must regenerate material with carbon element；
Step (4)：The regeneration carbon material powder for weighing 100g steps (3) preparation adds 100g simple substance sulphur powders in 600r/min
(ratio of grinding media to material after high-energy ball milling 6h under rotating speed：6: 1), you can high-performance lithium-sulfur cell carbon sulphur composite positive pole is obtained.
Button cell is assembled into using lithium-sulfur cell carbon sulphur composite positive pole manufactured in the present embodiment and lithium piece, its electrification
Learn performance as shown in the figure：
Fig. 1 is charge and discharge electrical schematic of the carbon sulphur composite positive pole for preparing under 1C multiplying powers, is compared under 1C discharge-rates
Capacity still has 888mAh g-1。
Fig. 2 is the discharge capacity circulation contrast of the lithium-sulfur cell carbon sulphur composite positive pole that embodiment 1 is prepared with comparative example
Figure, as can be seen from the figure material has excellent cycle performance, and the material circulation 80 under 1C discharge-rates encloses Posterior circle efficiency still
Have 99.9%, illustrate that the carbon sulphur composite for preparing has certain inhibitory action to polysulfide dissolving.
Embodiment 2
Step (1)：100kg waste and old lithium ion batteries are discharged, disassembled, isolated cathode pole piece is cut out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2)：Silk ribbon chips are placed in 1000L pure water and stir after ultrasound 6h, due to adhesive failure material with carbon element and
Copper Foil is separated, and by the removing Copper Foil that sieves, the solution of the carbon material powder for obtaining adds the ferric sulfate of 2000mol to be sufficiently stirred for
3h, the material with carbon element being filtrated to get is rinsed three times and filtered, filter cake vacuum at 100 DEG C with 15% volumetric concentration ethanol water again
Powder is broken into after drying, 150 mesh sieves is crossed and is obtained material with carbon element；
Step (3)：Weighing the carbon material powder after 0.5kg sieves adds 4kg potassium hydroxide high under 600r/min rotating speeds
Can ball milling 3h (ratios of grinding media to material：6: 1), mixed-powder is placed in argon gas atmosphere and activates 1.5h at 800 DEG C, reuse pure water rinsing three
Time, it is vacuum dried at 100 DEG C after filtration, powder is broken into, crossing 150 mesh sieves must regenerate material with carbon element；
Step (4)：The regeneration carbon material powder for weighing 100g steps (3) preparation adds 100g simple substance sulphur powders in 600r/min
(ratio of grinding media to material after high-energy ball milling 6h under rotating speed：6: 1), you can high-performance lithium-sulfur cell carbon sulphur composite positive pole is obtained.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, the specific volume under 1C discharge-rates
Amount still has 891 mAh g-1, Posterior circle efficiency is enclosed in circulation 80 under 1C discharge-rates still 99.9%.
Embodiment 3
Step (1)：100kg waste and old lithium ion batteries are discharged, disassembled, isolated cathode pole piece is cut out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2)：Silk ribbon chips are placed in 1000L pure water and stir after ultrasound 6h, due to adhesive failure material with carbon element and
Copper Foil is separated, and by the removing Copper Foil that sieves, the solution of the carbon material powder for obtaining adds the iron chloride of 2000mol to be sufficiently stirred for
3h, the material with carbon element being filtrated to get is rinsed three times and filtered, filter cake vacuum at 100 DEG C with 10% volumetric concentration ethanol water again
Powder is broken into after drying, 200 mesh sieves is crossed and is obtained material with carbon element；
Step (3)：Weigh the carbon material powder after 0.5kg sieves and add 4kg sodium chloride high energy under 600r/min rotating speeds
Ball milling 3h (ratios of grinding media to material：6: 1), mixed-powder is placed in argon gas atmosphere and activates 3h at 800 DEG C, reuse pure water and rinse three times, mistake
It is vacuum dried at 100 DEG C after filter, is broken into powder, crossing 200 mesh sieves must regenerates material with carbon element；
Step (4)：The regeneration carbon material powder for weighing 100g steps (3) preparation adds 100g simple substance sulphur powders in 600r/min
(ratio of grinding media to material after high-energy ball milling 6h under rotating speed：6: 1), you can high-performance lithium-sulfur cell carbon sulphur composite positive pole is obtained.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, the specific volume under 1C discharge-rates
Amount still has 880mAh g-1, Posterior circle efficiency is enclosed in circulation 80 under 1C discharge-rates still 99.7%.
Embodiment 4
Step (1)：100kg waste and old lithium ion batteries are discharged, disassembled, isolated cathode pole piece is cut out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2)：Silk ribbon chips are placed in 1000L pure water and stir after ultrasound 6h, due to adhesive failure material with carbon element and
Copper Foil is separated, and by the removing Copper Foil that sieves, the solution of the carbon material powder for obtaining adds the iron chloride of 2000mol to be sufficiently stirred for
3h, the material with carbon element being filtrated to get is rinsed three times and filtered with 10% volumetric concentration isopropanol water solution again, and filter cake is true at 100 DEG C
Sky is broken into powder after being dried, cross 200 mesh sieves；
Step (3)：Weigh the carbon material powder after 0.5kg sieves and add 4kg sodium chloride high energy under 600r/min rotating speeds
Ball milling 3h (ratios of grinding media to material：6: 1), mixed-powder is placed in argon gas atmosphere and activates 0.5h at 900 DEG C, reuse pure water and rinse three times,
It is vacuum dried at 100 DEG C after filtration, is broken into powder, crosses 200 mesh sieves；
Step (4)：The carbon material powder for weighing 100g steps (3) preparation adds 100g simple substance sulphur powder in 600r/min rotating speeds
(ratio of grinding media to material after lower high-energy ball milling 6h：6: 1), you can high-performance lithium-sulfur cell carbon sulphur composite positive pole is obtained.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, the specific volume under 1C discharge-rates
Amount still has 878mAh g-1, Posterior circle efficiency is enclosed in circulation 80 under 1C discharge-rates still 99.2%
Comparative example 1
Step (1)：Weigh 0.475kg graphite powders and 0.025kg conductive carbon blacks end adds 3kg potassium hydroxide in 600r/min
High-energy ball milling 3h (ratios of grinding media to material under rotating speed：6: 1), mixed-powder is placed in argon gas atmosphere and activates 3h at 800 DEG C, reuse pure water drift
Wash three times, be vacuum dried at 100 DEG C after filtration, be broken into powder, cross 150 mesh sieves；
Step (2)：The carbon material powder for weighing 100g steps (1) preparation adds 100g simple substance sulphur powder in 600r/min rotating speeds
(ratio of grinding media to material after lower high-energy ball milling 6h：6: 1), you can lithium-sulfur cell carbon sulphur composite positive pole is obtained.
The battery assembling of this comparative example resulting materials and method of testing are same as Example 1, test result such as Fig. 2 institutes
Show, specific capacity only has 680mAh g under 1C discharge-rates-1, the circle of circulation 80 Posterior circle efficiency only has under 1C discharge-rates
81%.
Comparative example 2
In this comparative example, the material with carbon element to reclaiming does not carry out activation process, specific as follows：
Step (1)：100kg waste and old lithium ion batteries are discharged, disassembled, isolated cathode pole piece is cut out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2)：Silk ribbon chips are placed in 1000L pure water and stir after ultrasound 6h, due to adhesive failure material with carbon element and
Copper Foil is separated, and by the removing Copper Foil that sieves, the material with carbon element being filtrated to get rinses three with 10% volumetric concentration isopropanol water solution again
Secondary and filter, filter cake is broken into powder after being vacuum dried at 100 DEG C, crosses 200 mesh sieves；
Step (3)：The carbon material powder for weighing 100g steps (2) preparation adds 100g simple substance sulphur powder in 600r/min rotating speeds
(ratio of grinding media to material after lower high-energy ball milling 6h：6: 1), you can lithium-sulfur cell carbon sulphur composite positive pole is obtained.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, the specific volume under 1C discharge-rates
Amount still has 850mAh g-1, the circulation 80 under 1C discharge-rates encloses Posterior circle efficiency and there was only 50%, the impurity copper ion of remaining and viscous
Knot agent reacts with the sulphur simple substance in material, and product causes extreme influence to the cycle performance of lithium-sulfur cell.
Claims (10)
1. a kind of Application way of waste and old lithium ion battery carbon material used as anode, it is characterised in that will be from waste and old lithium ion battery point
It is combined with sulphur from the regeneration material with carbon element for obtaining, lithium-sulfur cell carbon sulphur composite positive pole is obtained.
2. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 1, it is characterised in that including following
Step：
Step (1)：Discharge, disassemble, separating and to obtain cathode pole piece by waste and old lithium ion battery, will soak after the cathode pole piece cutting for obtaining
Stain is peeled off in water under ultrasound and/or stirring；Subsequently sieve, separate to obtain Copper Foil and material with carbon element suspension；
Step (2)：Ferric iron source is added in material with carbon element suspension, subsequently Jing separation of solid and liquid, washing, dry, broken, mistake successively
Sieve obtains material with carbon element；
Step (3)：Be incorporated in protective atmosphere under mixed with activator of the material with carbon element that step (2) is obtained activates；The product of activation
It is scrubbed, dry, crush, sieving must regenerate material with carbon element；
Step (4)：The regeneration material with carbon element that step (3) is obtained carries out ball milling mixing with elemental sulfur, and lithium-sulfur cell carbon sulphur is obtained
Composite positive pole.
3. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 2, it is characterised in that described three
Valency source of iron is water-soluble trivalent ferric salt.
4. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 2, it is characterised in that step (2)
In, for alcohol solution, in described alcohol solution, the volumetric concentration of alcohol is 5%～50% to the solvent that washing process is adopted.
5. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 4, it is characterised in that step (2)
In, the solvent that washing process is adopted is for ethanol water；In described ethanol water, the volumetric concentration of ethanol is 10%～
20%.
6. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 2, it is characterised in that described work
Agent is alkali metal hydroxide and/or salt.
7. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 6, it is characterised in that step (3)
In, the weight ratio of activator and material with carbon element is 1～10: 1.
8. the Application way of the waste and old lithium ion battery carbon material used as anode as described in claim 2 or 7, it is characterised in that step
(3) in, activation temperature is 800～900 DEG C, soak time is the time to be 0.5～3.0h.
9. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 2, it is characterised in that step (4)
In, it is 1: 0.1～1.1 to regenerate material with carbon element with the mass ratio of elemental sulfur.
10. the Application way of waste and old lithium ion battery carbon material used as anode as claimed in claim 2, it is characterised in that step
(3), the hybrid mode of step (4) is ball milling, and the rotating speed of ball milling is 300～800r/min；Ratio of grinding media to material is 1～6: 1.
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| CN109921124A (en) * | 2019-03-06 | 2019-06-21 | 四川大学 | A kind of recoverying and utilizing method of waste lithium ion cell anode material |
| CN111416170A (en) * | 2020-03-11 | 2020-07-14 | 长沙有色冶金设计研究院有限公司 | Method for recycling waste lithium ion battery negative electrode and co-producing conductive agent |
| US11837731B2 (en) | 2019-02-13 | 2023-12-05 | Lg Energy Solution, Ltd. | Cathode active material for lithium secondary battery |
| CN117637081A (en) * | 2024-01-26 | 2024-03-01 | 江苏杰成新能源科技有限公司 | Intelligent repair evaluation method for waste battery material |
| CN117637081B (en) * | 2024-01-26 | 2024-04-26 | 江苏杰成新能源科技有限公司 | Intelligent repair evaluation method for waste battery material |
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