CN106654439B - A kind of utilization method of waste and old lithium ion battery carbon material used as anode - Google Patents
A kind of utilization method of waste and old lithium ion battery carbon material used as anode Download PDFInfo
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- CN106654439B CN106654439B CN201710101487.6A CN201710101487A CN106654439B CN 106654439 B CN106654439 B CN 106654439B CN 201710101487 A CN201710101487 A CN 201710101487A CN 106654439 B CN106654439 B CN 106654439B
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Abstract
The invention discloses a kind of utilization methods of waste and old lithium ion battery carbon material used as anode, will be compound from the isolated regeneration carbon material of waste and old lithium ion battery and sulphur, and lithium sulfur battery anode material is made.Specially by waste and old lithium ion battery electric discharge, dismantling, binder fail in water removing, ferric iron source removal of impurities, activation, it is compound with elemental sulfur, finally be made lithium-sulfur cell carbon sulphur composite positive pole.The carbon material recycled using waste and old lithium ion battery is raw material, prepare the recovery scheme of high-performance lithium-sulfur battery composite cathode material, realize the high economic value added recycling of waste and old lithium ion battery carbon material used as anode, recovery efficiency is high, clean and environmental protection, the carbon sulphur composite positive pole being prepared receives sulphur ability strong, and high rate performance and cycle performance are excellent.
Description
Technical field
The present invention relates to the carbon material used as anode recovery technology fields in waste and old lithium ion battery, and in particular to a kind of to utilize 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 technique
Lithium ion battery since it has the shortcomings that high voltage, high-energy-density, long circulation life, from the nineties in last century with
To have obtained more and more extensive utilization in mankind's daily life.From 3C Product field originally at present electric car,
The extensive use of power grid 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, lithium ion battery cumulative production in China's 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%.It is about 1000 that China's power battery in 2015, which adds up learies,
Ton, it was predicted that the various power Vehicular battery learies in China will be more than 10,000 tons to the year two thousand twenty front and back.Contain in lithium ion battery
Elements and the organic electrolytes such as a large amount of copper, cobalt, nickel, necessarily will cause serious environmental pollution without processing after scrapping, and destroy
Ecological environment.But the elements such as the lithium, cobalt, nickel, the copper that are wherein rich in very big recycling be worth, therefore, waste and old lithium from
Sub- battery and the recycling and reusing for producing waste material have become countries in the world urgent need to solve the problem.
Currently, being concentrated mainly on the recovery and reuse technology of waste and old lithium ion battery to metals such as lithium, copper, cobalt, nickel
In recycling, and it is then relatively fewer for the recycling and reusing method of battery negative pole carbon material.Some recovery technologies will recycle
The Carbon anode arrived regains negative electrode for lithium ion battery slurry by the way of feed supplement.But in the preparation of lithium ion battery
In the process, for used battery material to constituent content, the index requests such as impurity concentration, granularity are stringent, the carbon materials recycled
Material is containing graphite, conductive carbon black and contains lithium solid electrolyte on a small quantity and is difficult to remove, therefore, using this method cathode material obtained
Material is difficult to meet the requirement as lithium ion battery negative material, it is used as again ion cathode material lithium will greatly shadow
The chemical property of lithium ion battery is rung.
Currently, most of recovery and utilization technology all only resides within the level of recycling, do not found for the carbon material of recycling
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 realize waste as Land use systems such as lubricating graphites utilizes.
Lithium-sulfur cell is the high-energy density secondary battery with application prospect with development potential, it has height ratio capacity
(1675mAh/g) and high-energy density (2600Wh/kg).Its positive electrode is mainly carbon sulphur composite material, and negative electrode material is gold
Belong to lithium.The carbon sulphur composite material of good, the big load sulfur content of stable structure, electric conductivity is that lithium-sulfur cell has excellent high rate performance and height
The key of specific capacity.Elemental sulfur is adsorbed on porous material skeleton, and the polysulfide in long-time cyclic process can dissolve
It is spread into electrolyte and through electrolyte, i.e. generation shuttle effect, leads to serious self discharge and capacity attenuation.Mesh
Before, in order to reduce shuttle effect as far as possible, lithium sulfur battery anode material, which needs to design complicated sandwich, carries out polysulfide
Physical absorption is needed materials 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 the prior art, waste and old lithium ion battery carbon material used as anode needs a kind of recycling with high economic value added
Technology.In addition, the carbon sulphur composite material of existing lithium-sulfur cell needs a kind of to prepare simple preparation method.
Summary of the invention
The present invention is relatively fewer for the recycling and reusing method of existing waste and old lithium ion battery carbon material used as anode, recycling
Carbon material shortage has the problems such as Land use systems of high economic value added, and the present invention provides a kind of waste and old lithium ion battery cathode
The utilization method of carbon material, it is intended to realize the high price recycling of lithium ion battery negative pole carbon material.
A kind of utilization method of waste and old lithium ion battery carbon material used as anode, will be isolated again from waste and old lithium ion battery
Raw carbon material and sulphur are compound, and lithium-sulfur cell carbon sulphur composite positive pole is made.
The inventors discovered that it is used as carbon raw material using from the recycling of waste and old lithium ion battery carbon material used as anode, regenerated material,
It is compound with sulphur simple substance, the carbon with good electrical performance/sulphur composite material can be made, the carbon/sulphur composite material is used as lithium sulphur electricity
The positive electrode in pond has good inhibiting effect to the dissolution of polysulfide, can express good electric property；For example, energy
It is obviously improved the cycle performance of lithium-sulfur cell.
In the present invention, the regeneration carbon material and sulphur simple substance that recycle from lithium ion battery are passed through into simple compound (mixing) i.e.
The lithium sulfur battery anode material with good electrical performance can be made, 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 larger impact to the performance of lithium sulfur battery anode material obtained.
By further investigation, the present inventor explores the utilization method of following waste and old lithium ion battery carbon material used as anode: will
Waste and old lithium ion battery is successively discharged, is disassembled, failure removing binder recycles to obtain useless carbon raw material in water, and carbon raw material of giving up is again
Through ferric iron source removal of impurities, activation, the composite positive pole of final obtained lithium-sulfur cell carbon sulphur compound with elemental sulfur.
It is of the present invention to utilize method, specifically includes the following steps:
Step (1): waste and old lithium ion battery is discharged, is disassembled, is separated and to obtain cathode pole piece, and obtained cathode pole piece is cut
After be impregnated in water, ultrasound and/or stirring under remove；It is then sieved, separates to obtain copper foil and carbon material suspension；
Step (2): ferric iron source being added into carbon material suspension, then successively through separation of solid and liquid, washing, drying, broken
Broken, sieving obtains carbon material；
Step (3): the carbon material that step (2) obtains is mixed with activator and is activated under protective atmosphere；Activation
Product is washed, dry, broken, be sieved to obtain regeneration carbon material；
Step (4): the regeneration carbon material and elemental sulfur that step (3) is obtained carry out ball milling mixing, and lithium-sulfur cell is made and uses
Carbon sulphur composite positive pole.
In the present invention, the cathode pole is removed under acid-free condition, carbon materials are made in the processing after through ferric iron source
Material activates the carbon material and activator, can be made to have and well receive sulphur performance, the regenerative carbon of the film containing lithium solid electrolyte
Material；Again originally by the compound obtained positive electrode as lithium-sulfur cell of obtained regeneration carbon material and sulphur.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 is discharged to termination electricity
It forces down in 1V.
In step (1), it is substantially discharged for example in salt discharge in water；The salt water is, for example, sodium-chloride water solution.
Waste lithium iron phosphate battery after being substantially discharged is disassembled, separates to obtain cathode pole piece；The cathode pole that will then obtain
At the fragment of silk ribbon shape after piece cutting.
Cathode pole piece after cutting is placed in water, removes adhesive failure under ultrasound and stirring.In the present invention, phase
It is compared to the binder removing mode of acid or alkali, the carbon material used as anode removed in water is more conducive to promote lithium-sulphur cell positive electrode
The electric property of material.
In step (1), ultrasonic frequency is 30~60kHz；The revolving speed of stirring is 100~500r/min.
In step (1), stirring under the parameter and under the synergistic effect of ultrasound, make negative electrode material completely, removing, it is real
The quick separating of existing negative electrode material and collector.
In step (1), ultrasound and stirring in water, until basic noresidue on copper foil.
In step (1), after the separation of negative electrode material and collector, sieving separating obtains copper foil and carbon material suspension.
In the present invention, by the processing of ferric iron source, the Cu during battery recycling can be removed2+Equal impurity；It avoids closing
At carbon/sulphur positive electrode contain undesired impurities, and then avoid lithium-sulfur cell self discharge.
Preferably, the 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 of iron chloride, ferric nitrate, ferric sulfate.
In step (2), ferric iron source, Fe in system are added into carbon material suspension3+Concentration be preferably 0.1~
5mol/L, further preferably 2mol/L.
In step (2), by ferric iron source, treated that system is separated by solid-liquid separation, and collecting and obtaining solid be the carbon after cleaning
Material；Carbon material after the removal of impurities is washed.
In step (2), the solvent that washing process uses is alcohol solution.
The inventors discovered that can effectively remove remaining organic adhesive in recycling carbon material using alcohol solution washing
Agent, and it is able to maintain being stabilized for solid electrolyte film.
Preferably, the volumetric concentration of alcohol is 5%~50% in the alcohol solution；Further preferably 10%~
20%.
The alcohol is can be with water infinitely than miscible small molecular alcohol.
Preferably, the alcohol is the unit or or polyalcohol of C2~4.
Further preferably, the alcohol is ethyl alcohol, isopropanol etc..
Still more preferably, the alcohol is ethyl alcohol.
Preferably, the solvent that washing process uses is ethanol water in step (2)；In the ethanol water,
The volumetric concentration of ethyl alcohol is 5%~50%；Further preferably 10%~20%.
Solid after the alcohol solution washing obtains carbon material through drying, broken, sieving；Preferably, described
Carbon material partial size be 100~300 mesh；Further preferably 150 mesh.
Preferably, the weight ratio of activator and carbon material is 1~10: 1 in step (3).
Further preferably, the weight ratio of activator and carbon material is 5~8: 1.
Preferably, the hybrid mode of activator and carbon material is ball milling.
Further preferably, in step (3), the revolving 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 revolving speed of ball milling is 600r/min；Ratio of grinding media to material is 6: 1.
Preferably, the activator is alkali metal hydroxide and/or salt.
Further preferably, the activator be the hydroxide of sodium, sodium salt, the hydroxide of potassium, in sylvite at least
It is a kind of.
Still more preferably, the activator is potassium hydroxide.
Preferably, activation process carries out under protective atmosphere.
The protective atmosphere is preferably nitrogen and/or inert gas.
The inert gas is, for example, helium, argon gas etc..
Preferably, activation temperature is 800~900 DEG C in step (3), activation time be 0.5~3.0h the time.
Further preferably, under the activation temperature, activation time be 0.5~1.5h the time.
Preferably, activator is mixed with carbon material and by weight for 1~10: 1 ratio lazy in step (3)
Property atmosphere, 0.5~1.5h is activated at 800~900 DEG C.
Under the collaboration of the preferred mass ratio, activation temperature and activation time, it can be made as subsequent immobilized elemental sulfur
Duct abundant is provided, improves the regeneration carbon material for carrying sulfur content, facilitates further to slow down lithium sulphur electricity through the activation processing
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, filter, be dried in vacuo after be broken into powder, be sieved to obtain regeneration
Carbon material.
Preferably, the partial size of the regeneration carbon material is 100~300 mesh；Further preferably 150 mesh.
Step (3) regeneration carbon material obtained is mixed with elemental sulfur；Preferably, in step (4), regeneration carbon material with
The mass ratio of sulphur simple substance is 1: 0.1~1.1.
Further preferably, the mass ratio for regenerating carbon material and sulphur simple substance is 1: 0.6~1.
Preferably, the hybrid mode of step (4) is ball milling, the revolving 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 revolving 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 and reusing method of waste and old lithium ion battery carbon material used as anode of the present invention, comprising the following steps:
Step (a): waste and old lithium ion battery being discharged, is disassembled, and pole piece is cut into silk by isolated cathode pole piece
Band-like fragment；
Step (b): silk ribbon chips are placed in pure water after stirring ultrasound 6h, due to adhesive failure carbon material and copper foil point
From by sieving removing copper foil, the solution of obtained carbon material powder is added trivalent iron salt and 3h is sufficiently stirred, the carbon being obtained by filtration
Material uses certain volume concentration ethanol aqueous solution to rinse and filter again, and filter cake is broken into powder, mistake after being dried in vacuo at 100 DEG C
Sieve；The volumetric concentration of ethyl alcohol is 5%~50% in ethanol water；The trivalent iron salt is ferric sulfate；
Step (c): a certain amount of potassium hydroxide is added in the carbon material powder after weighing sieving or sodium chloride carries out high energy ball
3h is ground, mixed-powder is placed in inert atmosphere and activates 0.5h at 800 DEG C, reuses pure water rinsing, is dried in vacuo and breaks after filtering
It is broken into powder, be sieved to obtain regeneration carbon material；Wherein, the add quality and the mass ratio of carbon material of potassium hydroxide or sodium chloride are 1
~10: 1；The revolving speed of the high-energy ball milling is 300~800r/min, and ratio of grinding media to material is (1~6): 1；
Step (d): the carbon material of step (c) preparation and elemental sulfur are mixed for 1: 0.8~1 in mass ratio, high-energy ball milling
After 6h, high-performance lithium sulphur battery carbon sulphur composite positive pole can be prepared by；The revolving speed of the high-energy ball milling is 300~800r/
Min, ratio of grinding media to material are (1~6): 1；.
Carbon sulphur composite material of the invention prepares lithium-sulfur cell as lithium sulfur battery anode material and carries out to its performance
The method of test: weighing the carbon sulphur composite material of above method preparation, and 5wt.%PVDF is used as binder, it is ground it is abundant after
A small amount of NMP is added and is mixed to form uniform black paste slurry, these slurries are coated in aluminum foil current collector as test electricity
Pole, with metal lithium sheet, electrode assembling becomes button cell as a comparison, use electrolyte system for LTFSI/DOL: DME (1:
1).Charging and discharging currents density used in test loop performance is 1000mA g-1(1C multiplying power).
The utility model has the advantages that
1, 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 can be prepared by the lithium sulfur battery anode material with good electrical performance by simple complex method.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 of parameter with sulphur, can further promote the electrical property of lithium sulfur battery anode material obtained
Energy.
2, the present invention overcomes waste and old lithium ion battery carbon material used as anode recycling and reusings to be worth low disadvantage, for recycling
High-quality carbon material provides the Land use systems of high economic value added, and technical solution is simple and easy.Battery material is generally active
The composition such as substance, conductive agent, binder, thickener, the recoverying and utilizing method, can take full advantage of recycling through the invention
Carbon negative pole material in contain high-quality graphite and conductive agent the characteristics of, no longer need to add after being prepared into lithium sulfur battery anode material
Conductive agent only need to add suitable thickener and binder can be prepared into positive pole plate of lithium-sulfur cell, improve the benefit of material
With rate, reduce costs.
3, the present invention also uses in the carbon material of recycling and exists containing lithium solid electrolyte, lithium-sulfur cell can be inhibited to be circulated throughout
The dissolution of polysulfide in journey, improves the cycle performance of lithium-sulfur cell.Therefore, height can be prepared using the carbon material used as anode of recycling
The lithium-sulfur cell carbon sulphur composite positive pole of performance.
Detailed description of the invention
[Fig. 1] is the charge and discharge electrical schematic of lithium-sulfur cell carbon sulphur composite positive pole prepared by embodiment 1.
[Fig. 2] is the discharge capacity circulation pair of lithium-sulfur cell carbon sulphur composite positive pole prepared by embodiment 1 and comparative example 1
Than figure.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention, and the protection scope of the claims in the present invention
It is not limited by the example.
Embodiment 1
Step (1): 100kg waste and old lithium ion battery being discharged, is disassembled, and isolated cathode pole piece cuts out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2): silk ribbon chips are placed in 1000L pure water stir ultrasound 6h after, due to adhesive failure carbon material and
Copper foil separation removes copper foil by sieving, and the ferric sulfate that 2000mol is added in the solution of obtained carbon material powder is sufficiently stirred
3h, the carbon material being obtained by filtration are used the rinsing of 15% volumetric concentration ethanol water three times again and are filtered, filter cake vacuum at 100 DEG C
It is broken into powder after drying, crosses 150 meshes and obtains carbon material powder；
Step (3): it is high under 600r/min revolving speed that 3kg potassium hydroxide is added in the carbon material powder after weighing 0.5kg sieving
(ratio of grinding media to material: 6: 1), mixed-powder is placed in argon atmosphere and activates 0.5h at 800 DEG C energy ball milling 3h, reuses pure water rinsing three
Time, it is dried in vacuo at 100 DEG C after filtering, is broken into powder, carbon material must be regenerated by crossing 150 meshes；
Step (4): 100g simple substance sulphur powder is added in 600r/min in the regeneration carbon material powder for weighing 100g step (3) preparation
(ratio of grinding media to material: 6: 1), it can be prepared by high-performance lithium-sulfur cell carbon sulphur composite positive pole after high-energy ball milling 6h under revolving speed.
Button cell is assembled into using lithium-sulfur cell carbon sulphur composite positive pole manufactured in the present embodiment and lithium piece, electrification
It is as shown in the figure to learn performance:
Fig. 1 is charge and discharge electrical schematic of the carbon sulphur composite positive pole of preparation under 1C multiplying power, is compared under 1C discharge-rate
Capacity still has 888mAh g-1。
Fig. 2 is that the discharge capacity of the lithium-sulfur cell carbon sulphur composite positive pole of embodiment 1 and comparative example preparation recycles comparison
Figure, as can be seen from the figure material have excellent cycle performance, under 1C discharge-rate material circulation 80 circle after cycle efficieny still
Have 99.9%, illustrates that the carbon sulphur composite material being prepared has certain inhibiting effect to polysulfide dissolution.
Embodiment 2
Step (1): 100kg waste and old lithium ion battery being discharged, is disassembled, and isolated cathode pole piece cuts out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2): silk ribbon chips are placed in 1000L pure water stir ultrasound 6h after, due to adhesive failure carbon material and
Copper foil separation removes copper foil by sieving, and the ferric sulfate that 2000mol is added in the solution of obtained carbon material powder is sufficiently stirred
3h, the carbon material being obtained by filtration are used the rinsing of 15% volumetric concentration ethanol water three times again and are filtered, filter cake vacuum at 100 DEG C
It is broken into powder after drying, crosses 150 meshes and obtains carbon material；
Step (3): it is high under 600r/min revolving speed that 4kg potassium hydroxide is added in the carbon material powder after weighing 0.5kg sieving
(ratio of grinding media to material: 6: 1), mixed-powder is placed in argon atmosphere and activates 1.5h at 800 DEG C energy ball milling 3h, reuses pure water rinsing three
Time, it is dried in vacuo at 100 DEG C after filtering, is broken into powder, carbon material must be regenerated by crossing 150 meshes；
Step (4): 100g simple substance sulphur powder is added in 600r/min in the regeneration carbon material powder for weighing 100g step (3) preparation
(ratio of grinding media to material: 6: 1), it can be prepared by high-performance lithium-sulfur cell carbon sulphur composite positive pole after high-energy ball milling 6h under revolving speed.
The battery assembly of the present embodiment resulting materials and test method are same as Example 1, the specific volume under 1C discharge-rate
Amount still has 891 mAh g-1, cycle efficieny still has 99.9% after 80 circles are recycled under 1C discharge-rate.
Embodiment 3
Step (1): 100kg waste and old lithium ion battery being discharged, is disassembled, and isolated cathode pole piece cuts out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2): silk ribbon chips are placed in 1000L pure water stir ultrasound 6h after, due to adhesive failure carbon material and
Copper foil separation removes copper foil by sieving, and the iron chloride that 2000mol is added in the solution of obtained carbon material powder is sufficiently stirred
3h, the carbon material being obtained by filtration are used the rinsing of 10% volumetric concentration ethanol water three times again and are filtered, filter cake vacuum at 100 DEG C
It is broken into powder after drying, crosses 200 meshes and obtains carbon material；
Step (3): 4kg sodium chloride high energy under 600r/min revolving speed is added in the carbon material powder after weighing 0.5kg sieving
(ratio of grinding media to material: 6: 1), mixed-powder is placed in argon atmosphere and activates 3h at 800 DEG C ball milling 3h, reuses pure water and rinses three times, mistake
It is dried in vacuo at 100 DEG C after filter, is broken into powder, carbon material must be regenerated by crossing 200 meshes；
Step (4): 100g simple substance sulphur powder is added in 600r/min in the regeneration carbon material powder for weighing 100g step (3) preparation
(ratio of grinding media to material: 6: 1), it can be prepared by high-performance lithium-sulfur cell carbon sulphur composite positive pole after high-energy ball milling 6h under revolving speed.
The battery assembly of the present embodiment resulting materials and test method are same as Example 1, the specific volume under 1C discharge-rate
Amount still has 880mAh g-1, cycle efficieny still has 99.7% after 80 circles are recycled under 1C discharge-rate.
Embodiment 4
Step (1): 100kg waste and old lithium ion battery being discharged, is disassembled, and isolated cathode pole piece cuts out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2): silk ribbon chips are placed in 1000L pure water stir ultrasound 6h after, due to adhesive failure carbon material and
Copper foil separation removes copper foil by sieving, and the iron chloride that 2000mol is added in the solution of obtained carbon material powder is sufficiently stirred
3h, the carbon material being obtained by filtration are used the rinsing of 10% volumetric concentration isopropanol water solution three times again and are filtered, and filter cake is true at 100 DEG C
It is broken into powder after sky is dry, crosses 200 meshes；
Step (3): 4kg sodium chloride high energy under 600r/min revolving speed is added in the carbon material powder after weighing 0.5kg sieving
Ball milling 3h (ratio of grinding media to material: 6: 1), mixed-powder is placed in argon atmosphere and activates 0.5h at 900 DEG C, reuses pure water and rinses three times,
It is dried in vacuo at 100 DEG C after filtering, is broken into powder, cross 200 meshes；
Step (4): 100g simple substance sulphur powder is added in 600r/min revolving speed in the carbon material powder for weighing 100g step (3) preparation
(ratio of grinding media to material: 6: 1), it can be prepared by high-performance lithium-sulfur cell carbon sulphur composite positive pole after lower high-energy ball milling 6h.
The battery assembly of the present embodiment resulting materials and test method are same as Example 1, the specific volume under 1C discharge-rate
Amount still has 878mAh g-1, cycle efficieny still has 99.2% after 80 circles are recycled under 1C discharge-rate
Comparative example 1
Step (1): weighing 0.475kg graphite powder and 3kg potassium hydroxide is added in 600r/min in 0.025kg conductive carbon black end
(ratio of grinding media to material: 6: 1), mixed-powder is placed in argon atmosphere and activates 3h at 800 DEG C high-energy ball milling 3h, reuses pure water drift under revolving speed
It washes three times, is dried in vacuo at 100 DEG C after filtering, be broken into powder, cross 150 meshes；
Step (2): 100g simple substance sulphur powder is added in 600r/min revolving speed in the carbon material powder for weighing 100g step (1) preparation
(ratio of grinding media to material: 6: 1), it can be prepared by lithium-sulfur cell carbon sulphur composite positive pole after lower high-energy ball milling 6h.
The battery assembly of this comparative example resulting materials and test method are same as Example 1, test result such as Fig. 2 institute
Show, specific capacity only has 680mAh g under 1C discharge-rate-1, cycle efficieny only has after 80 circles are recycled under 1C discharge-rate
81%.
Comparative example 2
It is specific as follows to the carbon material of recycling without being activated in this comparative example:
Step (1): 100kg waste and old lithium ion battery being discharged, is disassembled, and isolated cathode pole piece cuts out pole piece
It is cut into the fragment of silk ribbon shape；
Step (2): silk ribbon chips are placed in 1000L pure water stir ultrasound 6h after, due to adhesive failure carbon material and
Copper foil separation removes copper foil by sieving, and the carbon material being obtained by filtration uses 10% volumetric concentration isopropanol water solution to rinse three again
Secondary and filter, filter cake is broken into powder after being dried in vacuo at 100 DEG C, crosses 200 meshes；
Step (3): 100g simple substance sulphur powder is added in 600r/min revolving speed in the carbon material powder for weighing 100g step (2) preparation
(ratio of grinding media to material: 6: 1), it can be prepared by lithium-sulfur cell carbon sulphur composite positive pole after lower high-energy ball milling 6h.
The battery assembly of the present embodiment resulting materials and test method are same as Example 1, the specific volume under 1C discharge-rate
Amount still has 850mAh g-1, cycle efficieny only has 50% after 80 circles are recycled under 1C discharge-rate, remaining impurity copper ion 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 (9)
1. a kind of utilization method of waste and old lithium ion battery carbon material used as anode, which is characterized in that will be from waste and old lithium ion battery point
It is compound from obtained regeneration carbon material and sulphur, lithium-sulfur cell carbon sulphur composite positive pole is made；The following steps are included:
Step (1): waste and old lithium ion battery is discharged, is disassembled, is separated and to obtain cathode pole piece, is soaked after obtained cathode pole piece is cut
Stain Yu Shuizhong is removed under ultrasound and/or stirring；It is then sieved, separates to obtain copper foil and carbon material suspension；
Step (2): ferric iron source being added into carbon material suspension, then successively through separation of solid and liquid, washing, drying, broken, mistake
Sieve obtains carbon material；
Step (3): the carbon material that step (2) obtains is mixed with activator and is activated under protective atmosphere；The product of activation
It is washed, dry, broken, be sieved to obtain regeneration carbon material；
Step (4): the regeneration carbon material and elemental sulfur that step (3) is obtained carry out ball milling mixing, and lithium-sulfur cell carbon sulphur is made
Composite positive pole.
2. the utilization method of waste and old lithium ion battery carbon material used as anode as described in claim 1, which is characterized in that described three
Valence source of iron is water-soluble trivalent ferric salt.
3. the utilization method of waste and old lithium ion battery carbon material used as anode as claimed in claim 2, which is characterized in that step (2)
In, the solvent that washing process uses is alcohol solution, and in the alcohol solution, the volumetric concentration of alcohol is 5% ~ 50%.
4. the utilization method of waste and old lithium ion battery carbon material used as anode as claimed in claim 3, which is characterized in that step (2)
In, the solvent that washing process uses is ethanol water；In the ethanol water, the volumetric concentration of ethyl alcohol is 10% ~ 20%.
5. the utilization method of waste and old lithium ion battery carbon material used as anode as described in claim 1, which is characterized in that the work
Agent is alkali metal hydroxide and/or alkali metal salt.
6. the utilization method of waste and old lithium ion battery carbon material used as anode as claimed in claim 5, which is characterized in that step (3)
In, the weight ratio of activator and carbon material is 1 ~ 10:1.
7. the utilization method of waste and old lithium ion battery carbon material used as anode as described in claim 1 or 6, which is characterized in that step
(3) in, activation temperature be 800 ~ 900 DEG C, activation time be 0.5 ~ 3.0h the time.
8. the utilization method of waste and old lithium ion battery carbon material used as anode as described in claim 1, which is characterized in that step (4)
In, the mass ratio for regenerating carbon material and elemental sulfur is 1:0.1 ~ 1.1.
9. the utilization method of waste and old lithium ion battery carbon material used as anode as described in claim 1, which is characterized in that step (3),
The hybrid mode of step (4) is ball milling, and the revolving speed of ball milling is 300 ~ 800r/min；Ratio of grinding media to material is 1 ~ 6:1.
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