CN113258159A - Device and method for regenerating lithium ion battery electrode material - Google Patents
Device and method for regenerating lithium ion battery electrode material Download PDFInfo
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- CN113258159A CN113258159A CN202110489715.8A CN202110489715A CN113258159A CN 113258159 A CN113258159 A CN 113258159A CN 202110489715 A CN202110489715 A CN 202110489715A CN 113258159 A CN113258159 A CN 113258159A
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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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- 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 provides a device and a method for regenerating an electrode material of a lithium ion battery, which utilize the characteristic of instant discharge of a capacitor to generate a large amount of Joule heat in second-level time under the atmosphere of normal pressure air so as to remove impurities of the waste electrode material between electrodes; putting the waste electrode material into a reaction device and vacuumizing; after the capacitor is selected, the capacitor is charged by using a direct current stabilized voltage supply; and discharging after charging to a predetermined voltage. The device designed by the invention is simple and safe, consumes less energy, and the regenerated waste electrode material has simple steps, can complete the regeneration of the electrode material in one step and has excellent electrochemical performance.
Description
Technical Field
The invention relates to a device and a method for regenerating an electrode material of a lithium ion battery.
Background
In the times that the market scale of new energy products is gradually increased, the annual output of lithium ion batteries in China reaches hundreds of billions, but the waste lithium ion batteries after long-time use are difficult to treat and cannot be reused, the waste lithium ion batteries contain a large amount of heavy metals (iron, nickel, cobalt, copper, aluminum and the like), and meanwhile, a large amount of organic waste liquid (electrolyte and the like) is contained in the batteries, so that irreversible damage is easily caused to the environment, and the separated waste electrode materials cannot be reused. At present, in the recovery method for lithium iron phosphate and the ternary battery with the largest market scale, after the electrode material is mainly separated by ultrasonic in solution, the electrode material is recovered by using a high-temperature solid phase method or a chemical separation method, the steps are complicated, the environment is damaged, and the electrochemical performance of the recovered electrode material is low. The main problems of the prior art are as follows:
high-temperature solid phase method: when the method is used for recovering the anode material (lithium iron phosphate, ternary material and the like), the anode material needs to be calcined for multiple times in different gas atmospheres: calcining in an oxidizing gas atmosphere to remove a conductive agent and a binder in the electrode material, and then supplementing salts containing iron, nickel, cobalt, manganese and lithium after determining the proportion of the material elements and calcining in inert gas atmosphere at different temperatures for multiple times; when the negative electrode material (such as graphite) is recovered, the negative electrode material needs to be calcined at multiple stages and different temperatures in an inert gas atmosphere to remove elements such as lithium, iron and the like, a binder and electrolyte in the graphite;
the technical problem of the high-temperature solid phase method is as follows: the high-energy consumption heating and heat-preservation calcining functions are realized, the high-purity inert gas is used for protection, and the electrochemical performance of the product is low due to the change of the crystal structure of the material caused by the continuous high temperature;
chemical separation method: when the positive electrode material is recovered, the positive electrode material (lithium iron phosphate, ternary material and the like) is dissolved by strong acid, impurities in the material are removed, then strong base is used for precipitation, and calcination and forming in an inert gas atmosphere are needed after ball milling; the negative electrode material (graphite, etc.) needs to be subjected to impurity separation by strong acid, and is subjected to ball milling and drying after being washed for multiple times;
the technical problem of the chemical separation method is as follows: the method needs to use a large amount of acid and alkali for recovery, generates a large amount of waste liquid, causes secondary damage to the environment, is long in time consumption (dissolution, precipitation and recrystallization), and has low electrochemical performance
Disclosure of Invention
In order to solve the problems, the following invention concepts are proposed: applying direct current to two ends of the waste electrode material to perform instantaneous large-current direct current discharge, utilizing the poor conductor characteristics of the waste electrode material to generate joule heat inside, and instantaneously heating to a certain temperature to volatilize impurities in the electrode material. (instantaneous high energy impact).
The invention has the following conception characteristics:
1. instantaneous ultra-high energy impurity removal
The method of chemical reduction (change of internal bond energy) or high-temperature thermal reduction (continuous application of thermal energy) is used for removing electrolyte, a passivation film and redundant dead lithium in the waste electrode material by volatilization or acid-base reaction.
2. The reaction product with instant ultrahigh energy recovery has low impurity content, no change in crystal structure and good electrochemical performance
No medium, acid and alkali solution are introduced, thus fundamentally solving the problems of solid-liquid separation, drying, generation of waste liquid and the like; because the reaction temperature is distributed uniformly, impurities are removed more completely, and the conductivity is high; the reaction of controlling a certain temperature can keep good electrochemical performance without changing the crystal structure of the material.
3. The instant ultrahigh energy reaction allows the reduction reaction to be carried out in the atmosphere of normal pressure air without oxygen-free environment protection
The transient high temperature reaction that occurs under a transient (second-order) high energy strike enables the reduction of the reactant species to be accomplished without any reaction with oxygen in the air, thus eliminating the need for oxygen-free protection in an inert gas or vacuum environment.
4. Compared with the traditional high-temperature thermal reduction method, the energy consumption of the instant ultra-high energy impact is reduced
Because the reaction is completed instantly, heat is mainly transferred in the material in a black body radiation mode, and the reduction process is nearly adiabatic reaction, the heat loss is extremely small, and the energy consumption is ultralow compared with the traditional high-temperature reduction process of long-time temperature rise and heat preservation;
the following key technical problems need to be solved for realizing the conception of the invention
1. Obtaining instantaneous ultrahigh energy;
it is difficult to obtain instantaneous ultra high energy that satisfies the requirements of the inventive concept in the prior art. The realization of ultra-high energy usually needs ultra-high power electric appliances, but the traditional ultra-high power electric appliances can not achieve instantaneous energy release in practical application, and only can continuously apply high energy to materials, such as: the long-time high-voltage treatment at two ends of the material can heat the material or convert electric energy into heat energy through a high-temperature resistor to generate energy, and the like, so that the aim of reducing the stacking of the graphene oxide layers by ultra-short-time heat treatment cannot be fulfilled, and the energy consumption cannot be reduced; the ultrahigh energy instantaneously released by a high-power electric appliance cannot be accurately released or controlled through a program, and not only accurate reduction but also safe production cannot be realized in production.
The instant ultra-high energy required in the inventive concept is the instant high energy generated by the high current passing through the material when the circuit is switched on. Considering that current propagation can occur at the moment of circuit connection, the speed can reach 300000km/s, the most direct mode can be that an industrial high-power supply is used for carrying out instant electrification on a reaction substance, but the reaction circuit is connected to a power grid in such a mode, the power grid is easy to damage by instant high current, and due to the high resistance of the reaction substance, the high-voltage direct-current power supply and the high-voltage power grid which are about one hundred thousand volts are needed for realizing the instant high-temperature current of thousands of amperes, and a high-voltage resistant relay is needed for connecting a switch, so that the cost is immeasurable; it is also a way to achieve large current spread by momentary short-circuiting, but each short-circuiting reaction causes irreversible damage to the circuit.
Through repeated tests and modification of the technical scheme, the following technical achievements are obtained: the reaction is carried out by utilizing the characteristic of instantaneous discharge of the capacitors, instantaneous high-current discharge is generated by adopting a mode of connecting a plurality of capacitors in series and in parallel, ultrahigh energy is generated, and the reaction can be carried out in the atmosphere of normal pressure air without oxygen-free protection under the inert gas atmosphere or vacuum environment. The mode of setting up the relay regulates and controls the size of the energy of releasing. The power supply system is composed of a plurality of capacitors in series and parallel connection, the capacitors are charged (or charged in other modes) by using a direct current power supply, the charging voltage and the number selection of the capacitors are controlled by a logic control switch, the charging voltage of the capacitors is consistent by a voltage equalizing circuit, and a protection circuit is added to prevent a large current generated instantaneously from damaging the circuit. The discharge voltage, discharge capacity, discharge time, pulse frequency and the like of the capacitor can be regulated and controlled (or controlled and monitored by using a program circuit such as a singlechip and the like) through a logic control switch or other modes. When the capacitor discharges, the electric energy stored by the capacitor is used for discharging, the reaction system is independent of a power supply system of a power grid, and the reaction system can be connected with the power grid to supplement the electric energy after the discharging is finished, so that the high voltage and instantaneous high temperature and high current during the reaction can not cause any influence on the power grid; the method realizes the reduction of the graphene oxide with different qualities by electric shocks with different energies, and provides an idea for industrial production.
2: a medium for releasing the instantaneous ultra-high energy to the material;
it is difficult to obtain a medium in the prior art that satisfies the instantaneous ultra-high energy release to the material required in the inventive concept. When ultra-high energy is applied to a material by means of a capacitor that momentarily discharges a high current, it is necessary to connect the material to a circuit. If the circuit cable is directly connected to two ends of the material, the problems of short circuit and the like caused by melting of a copper wire of the cable due to high temperature can be caused;
the medium required for releasing the instantaneous ultra-high energy in the inventive concept should be an electrode. But the electrode is melted when ultrahigh temperature is generated instantly, the active reductive metal electrode and the electrode material generate reduction reaction, the material is changed to be active oh enough, and the silkworm feeding electrode is continuously fed; the use of relatively inert metal electrodes results in energy loss in the lines due to excessively high resistivity, and the purpose of ultra-high energy transmission cannot be achieved. Commonly used electrodes include: copper, tungsten, platinum, alloy electrodes, and the like. Copper can enable energy to have no loss basically in the transmission process, but instantaneous high temperature can cause melting of copper, electrodes can be damaged after the copper is used for many times, and the copper is used as metal with strong reducibility, is easy to perform reduction reaction with electrode materials in the reaction process, and introduces metal impurities; the tungsten electrode has a high melting point but a resistivity of 5.48X 10-8Omega m is 5 times of copper, so that energy loss is easily caused; the platinum electrode is used as a noble metal electrode, has a lower melting point and a resistivity close to that of copper, but has high manufacturing cost and is easy to damage at high temperature; the remaining alloy electrodes have related technical problems.
It is therefore a technical challenge to obtain a medium that satisfies the instantaneous ultra-high energy release to the material required in the inventive concept.
Through repeated tests and modification of the technical scheme, the following results are obtained: on the premise of no circuit energy loss, no impurity introduction, electrode recycling, cost control and the like, the graphite rod is adopted at the contact end, and the tail end of the graphite rod is connected with the copper rod to serve as an electrode. Graphite has a low specific resistance as a contact electrode, and can protect the electrode with a small energy loss without introducing metal impurities in multiple reactions. Quartz tube or other high temperature resistant material is selected as a reaction container, two ends of the output line are connected to two ends of the graphite electrode to be used as a reactor, and the tightness degree of the material during reaction is adjusted.
The specific research scheme of the invention is as follows:
the graphene reduction and oxidation device comprises a reactor and a power supply system, wherein the reactor comprises an outer protective shell, a first input line and a second input line of a cable are introduced into two sides of the outer protective shell and are connected with a first conductive copper disc and a second conductive copper disc, two sides of an inner device are provided with a first load copper disc and a second load copper disc, the bottom of the inner device is provided with an insulating bakelite support frame, a positive conductive copper rod and a negative conductive copper rod are erected in the centers of two sides of the support frame in a perforation mode, one ends of the positive conductive copper rod and the negative conductive copper rod penetrate through the first conductive disc, the second conductive disc, the first load disc and the second load disc, the other ends of the positive conductive copper rod and the negative conductive copper rod are subjected to grooving treatment, one ends of the positive graphite rod and the negative graphite rod are tightly connected to the grooves of the conductive copper rods, the other ends of the positive graphite rod and the negative graphite rod are in contact with a reaction material, the reaction material is placed into a quartz tube, and the positive graphite rod and the negative graphite rod and the reaction electrode are placed into the quartz tube as a reaction electrode;
the power supply system comprises a capacitor charging power supply, an energy system and a release circuit:
capacitor charging power supply: setting voltage regulation potentiometer by using adjustable DC regulated power supply or by using DC regulated power supply parallel resistor, connecting protective resistor in series at power supply end, and setting charging voltage and ammeter V1、A1Switching on and off a charging power supply in a relay mode;
an energy system: an adjustable direct current stabilized power supply is connected with a system in series, a plurality of capacitors are connected in parallel or in series to obtain an ultra-high energy release system, and capacitance voltmeters V are arranged at two ends of the system2Parallel high-power heat-release resistor R2As a residual energy release circuit;
the release circuit is set up: IGBT or silicon-controlled module circuit is used as a switch path for releasing energy, a driving power supply is additionally arranged to supply power to the module, and because of the low resistance and high conductivity of electrode materials, a constantan wire connected in series with 0.5 omega is used as a heat-releasable resistor R3Preventing the circuit from short circuiting.
The method for recycling the waste electrode material comprises the following steps:
the method comprises the following steps: processing waste electrode materials by separating from a current collector, then loading a sample into a reactor, connecting a positive graphite rod and a negative stone grinding rod at two ends, and connecting an adjusting material with an electrode in a contact manner;
step two: adjusting 50J to 1200J energy per 100mg waste electrode material for striking, and adjusting the relation between the capacitor capacity and the voltage through a formula 1 to enable the capacitor to reach corresponding energy
Opening DC voltage-stabilized power supply and capacitor charging switch K1And KCnTurning off the circuit when the voltage reaches a preset voltage;
step three: opening capacitor energy release switch K3The flash phenomenon occurs within one second, the reaction is finished, the residual energy which is not released in the capacitor is released, namely the switch K is cut off3Opening residual energy release switch K2And repeating the step two, and performing energy beating on the product for 1 to 5 times to finally obtain the product.
Description of the technology
Compared with the prior art, the invention has the beneficial effects that:
1. the device adopted by the invention has lower cost, has smaller occupied space and purchase cost compared with a high-temperature solid phase method and a chemical separation method, does not need the protection of inert gas or other gas atmosphere, saves related cost and is easier to realize industrialization;
2. the method adopts the instantaneous electric heating to regenerate the waste battery electrode material, the high-temperature solid phase method and the chemical separation method all need more time to carry out reaction or heat preservation, and the method can regenerate quantitative electrode material only in second-level time, thereby further reducing the production cost and improving the yield;
3. the method designed by the invention is relatively safe, strong acid and strong base which are harmful to human bodies and environment are not used, a high-power supply and industrial high-voltage electricity are not used, and the safety of operators can be ensured in production.
Drawings
FIG. 1 is a sectional view: elevation of the reactor centerline in cut section;
fig. 2 is a sectional view: a left view along the bakelite support frame centerline in the reactor;
FIG. 3 is a pictorial representation: (a) the device panel of the present invention; (b) the reaction apparatus of the present invention; (c) panel display when 5 capacitors are charged to 200V; (d) flash light generated at the moment of reaction;
FIG. 4 is a scanning electron microscope image of a waste battery anode material lithium iron phosphate;
FIG. 5 is a scanning electron microscope image of a regenerative battery anode material lithium iron phosphate;
6-7 are electrochemical rate performance and cyclic voltammetry curves of a button cell assembled from a regenerated material obtained by striking 2 capacitors for 3 times at 200V;
8-9 are electrochemical rate performance and cyclic voltammetry curves of a button cell assembled from a recycled material obtained by striking 1 capacitor at 200V for 3 times;
FIGS. 10-11 are electrochemical rate performance and cyclic voltammetry curves of a button cell assembled from a recycled material obtained by striking 1 capacitor at 200V for 1 time;
fig. 12 to 14 are electrochemical rate performance, cyclic voltammetry curve and first to fifth charge and discharge curves of a button cell assembled by using 1 capacitor and beating 3 times under 150V voltage;
15-16 are electrochemical rate performance and cyclic voltammetry curves of a button cell assembled from recycled materials obtained after 1 capacitor is used and hit for 5 times at 200V;
FIG. 17 is a cyclic voltammetry test performed at a small sweep rate after assembling the materials obtained above into a coin cell;
FIGS. 18(a) and (b) are transmission electron micrographs of graphite, which is a negative electrode material of a used battery; (c) and (d) is a transmission electron micrograph of the recycled material graphite obtained by striking the recycled material at 200V for 1 time by using 2 capacitors; (e) and (f) is a transmission electron micrograph of the recycled material graphite obtained by striking the recycled material 1 time at 200V using 5 capacitors; (g) and (h) is a transmission electron microscope image of the recycled material graphite obtained by striking the recycled material graphite for 1 time at 200V by using 10 capacitors;
FIG. 19 shows Raman measurements performed on the regenerated graphite material obtained by electric shock under different conditions;
FIG. 20 is a gas adsorption specific surface area test of the regenerated material graphite obtained by 1 hit at 200V using 10 capacitors;
FIG. 21 is a comparison of electrochemical performance rate tests of button cells assembled from graphite, a recycled material, obtained by electric shock under different conditions, and graphite, a commercial negative electrode material;
fig. 22 is a cyclic voltammetry test performed on the regenerated material graphite obtained by 1 hit at 200V using 10 capacitors.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention discloses a device and a method for regenerating waste battery electrode materials quickly, efficiently, with low cost and environmental protection. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. Such as adding or subtracting individual capacitors or modifying control capacitor circuits, or changing reaction devices, are within the scope of the present invention.
Example 1:
a device for reducing graphene oxide comprises a reactor 1 and a power supply system, wherein the reactor 1 comprises an outer protective shell 101 with the size of 4000mm by 200mm by 300 mm; the method is characterized in that: using a high-temperature-resistant acrylic material, and opening a hole at the center of 50mm away from the bottom at two sides for 10mm to lead in a cable; the 25 mm square cable inputs 102, 103 are connected to the housing 101 using threaded holes(ii) a The jacks are connected with conductive copper discs 104 and 105, the diameter of each conductive copper disc is 30mm, the jacks 102 and the jacks 103 are respectively connected through cold pressing terminals, and the diameter of a central hole is 8 mm; the load copper discs 106 and 107 are connected through the jacks, the diameter is 30mm, and the diameter of a central opening is 8 mm; the center of each side of the insulating bakelite support frame 108 is provided with a hole of 8mm, and the insulating bakelite support frame is fixed at the bottom of the support frame 101 in an adhesive manner; the positive and negative conductive copper bars 109 and 110 are 120mm long and 8mm in diameter, one end of each copper bar penetrates through 108 supporting frames and is connected with 104 and 105 through threaded holes to be connected with a circuit, and a groove 5mm deep and 3.8mm in diameter is dug in the center of the other end of each copper bar; positive and negative graphite rods 111 and 112 with the length of 30mm and the diameter of 3.8mm are connected with the grooves of the 109 and 110 conductive copper rods, and the other ends of the positive and negative graphite rods are contacted with the reaction material; a high-temperature resistant quartz tube 113 with the diameter of 4mm and the wall thickness of 2mm is placed into the quartz tube with 111 and 112 stone grinding rods as reaction electrodes. The power supply system comprises a capacitor charging power supply and is characterized in that a direct-current stabilized power supply is used: the capacitor is charged at 0-350V and the charging voltage is less than the rated voltage of the capacitor, and a protective resistor R is connected in series at two ends of the power supply1(120 Ω × 2, 500W); the energy system is characterized in that a plurality of capacitors are connected in series or in parallel for energy storage, in the embodiment, 10 capacitors 5600mF and with the rated voltage of 400V are connected in parallel (C1-C10), and a high-power heat release resistor R is connected in parallel at the end of a capacitor bank2(1000 Ω, 500W) as a residual energy release circuit; the release circuit is characterized in that an IGBT (silicon controlled rectifier) module circuit is used as a switch for releasing energy, a 12V driving power supply is independently arranged, and a constantan wire of 0.5 omega is connected in series on an output circuit and used as a heat-release resistor R3。
The method comprises the following steps: directly physically separating and crushing a waste battery anode material (lithium iron phosphate);
step two: weighing 100mg of the powder obtained in the step one, directly adding the powder into a quartz tube 113, and putting the quartz tube into a reaction device;
step three: turning on a direct current power supply, selecting capacitors C1 and C2, and charging to 200V;
step four: after the charging reaches the preset voltage, a charging button is closed, a discharging button is pressed, the striking energy is 224J, and the process is repeated for 3 times;
step five: taking out the quartz tube and the electrode to obtain a regenerated anode material lithium iron phosphate, mixing the material with the binder and the conductive agent, coating the mixture on an aluminum foil, assembling a button cell, and carrying out electrochemical performance test, wherein the performance is poor, the specific capacity is only 23mAh/g under low current, and the deviation of a reduction peak and an oxidation peak in a cyclic voltammetry curve is serious as shown in figures 4 and 5.
Example 2:
this example is substantially the same as example 1 except that in step three, the capacitor is selected to be C1, i.e. 112J energy is used to hit for 3 times, and electrochemical performance is shown in fig. 6 and 7, the performance is poor, the specific capacity is 90mAh/g under a small current, and the reduction peak and the oxidation peak in the cyclic voltammetry curve are severely shifted.
Example 3:
this example is substantially the same as example 2, except that the striking number in the fourth step is 1, i.e. striking 1 with energy of 112J, and electrochemical properties as shown in fig. 7 and 8 are obtained, the performance is poor, the specific capacity is 100mAh/g under a small current, and the reduction peak and the oxidation peak in the cyclic voltammetry curve are severely shifted.
Example 4:
this embodiment is substantially the same as embodiment 3, except that in step three, the charging voltage is 150V; the striking frequency in the fourth step is 3 times, namely striking is performed for 3 times by using 63J energy, so that electrochemical properties such as shown in fig. 10, 11 and 12 are obtained, the performance is good, the specific capacity is 150mAh/g under low current, the reached theoretical capacity is 88%, the circulation is stable, the deviation in a cyclic voltammetry curve is small, and in a comparison graph of a small-sweep-speed cyclic voltammetry curve in fig. 15, the redox peak of the group of materials is closest to the theoretical peak position of the lithium iron phosphate battery, the peak area is maximum, and the best electrochemical properties are obtained.
Example 5:
this example is substantially the same as example 4, except that the striking number in the fourth step is 5, i.e. striking 5 times with 63J energy, and electrochemical performance as shown in fig. 13 and 14 is obtained, the performance is poor, the specific capacity is only 110mAh/g under a small current, and the reduction peak and the oxidation peak in the cyclic voltammetry curve are severely shifted.
Example 6:
this example is substantially the same as example 1, except that in the first step, the positive electrode material of the waste battery is replaced by the negative electrode material (graphite) of the waste battery; the number of strokes in step four is 1, i.e. 1 stroke with 224J of energy. The product obtained by the embodiment has low impurity removal degree, and the graphite agglomeration is still serious.
Example 7:
this example is substantially the same as example 6, except that in step three, capacitors C1, C2, C3, C4, and C5 were selected for charging and reaction, and the impact energy was 560J. The product obtained by the embodiment has high impurity removal degree, low graphite order degree and low electrochemical performance.
Example 8:
this example is substantially the same as example 7 except that in step three, capacitors C1-C10 were selected for charging and reaction, and the striking energy was 1120J. The impurities of the produced sheet obtained by the embodiment are completely removed, the specific surface area is recovered to the initial graphite state, and the electrochemical performance is good.
The transmission electron microscope image in fig. 16 can clearly show that the graphite agglomerated together is gradually opened along with the increase of the impact energy, and the binder and the electrolyte are gasified along with the high temperature.
FIG. 17 shows that the materials obtained in examples 6, 7 and 8 and graphite which is a negative electrode material of a waste battery are subjected to Raman tests, and the Raman tests are carried out according to the increase of electric shock energy Id/IgThe degree of order of the graphite material increases with decreasing value of (a).
FIG. 18 shows that the specific surface area of the material obtained in example 8, which was recovered to the level of original graphite, was 68.345m3/g。
Fig. 19 is a comparison of electrochemical performance of the button cell in examples 6, 7 and 8 with that of a waste battery and a commercial negative electrode material graphite battery, and the material obtained in example 8 is found to be substantially consistent with the performance of the commercial negative electrode material graphite and to be more stable.
Fig. 20 is a cyclic voltammogram test of the coin cell in example 8 at a small scan rate, and the first cyclic voltammogram clearly shows the formation of the SEI film.
The invention provides a device and a method for regenerating waste lithium ion battery electrode materials quickly, environmentally and efficiently, which utilize the characteristic of instantaneous discharge of a capacitor to generate a large amount of Joule heat in second-level time under the atmosphere of normal pressure air to remove impurities of the waste electrode materials between electrodes; putting the waste electrode material into a reaction device and vacuumizing; after the capacitor is selected, the capacitor is charged by using a direct current stabilized voltage supply; and discharging after charging to a predetermined voltage. The device designed by the invention is simple and safe, consumes less energy, and the regenerated waste electrode material has simple steps, can complete the regeneration of the electrode material in one step and has excellent electrochemical performance.
Claims (5)
1. An apparatus for regenerating an electrode material for a lithium ion battery, comprising: the reactor comprises a reactor (1) and a power supply system, wherein the reactor (1) comprises an outer protective shell (101), a first input line (102) and a second input line (103) of a cable are introduced into two sides of the outer protective shell (101), the first conductive copper disc (104) and the second conductive copper disc (105) are connected, a first load copper disc (106) and a second load copper disc (107) are arranged on two sides of an internal device, an insulating bakelite support frame (108) is arranged at the bottom of the internal device, an anode conductive copper rod (109) and a cathode conductive copper rod (110) are erected in the centers of two sides of the support frame (108) in a perforation mode, one end of the anode conductive copper rod (111) and one end of the cathode graphite rod (112) are closely connected to a groove of the conductive copper rod, the other end of the graphite rod is contacted with a reaction material, the reaction material is placed into a high-temperature resistant quartz tube (113), a positive graphite rod (111) and a negative graphite rod (112) are placed into the quartz tube to serve as reaction electrodes, and the reaction material is lithium iron phosphate, a ternary material and graphite;
the power supply system comprises a capacitor charging power supply, an energy system and a release circuit:
capacitor charging power supply: method for using adjustable DC stabilized power supply or using DC stabilized power supply parallel resistorThe voltage regulating potentiometer is arranged in a mode that a protective resistor is connected in series at a power supply end, and charging voltage and an ammeter V are arranged1、A1Switching on and off a charging power supply in a relay mode;
an energy system: an adjustable direct current stabilized power supply is connected with a system in series, a plurality of capacitors are connected in parallel or in series to obtain an ultra-high energy release system, and capacitance voltmeters V are arranged at two ends of the system2Parallel high-power heat-release resistor R2As a residual energy release circuit;
the release circuit is set up: IGBT or silicon-controlled module circuit is used as a switch path for releasing energy, a driving power supply is additionally arranged to supply power to the module, and because of the low resistance and high conductivity of electrode materials, a constantan wire connected in series with 0.5 omega is used as a heat-releasable resistor R3Preventing the circuit from short circuiting.
2. The apparatus of claim 1, wherein the apparatus comprises: the outer protective shell (101) is made of acrylic materials.
3. A method of regenerating an electrode material for a lithium ion battery, comprising the steps of:
the method comprises the following steps: the method comprises the following steps of (1) loading waste battery electrode material powder into a quartz tube (113) in a reactor (1);
step two: using a power supply system to supply selected capacitors C1-nAfter charging to a preset voltage, closing a charging button;
step three: turning on the discharge button, completing the reaction, turning off the switch K3Opening residual energy release switch K2And releasing residual energy which is not released in the capacitor, repeating the step two, and performing multiple times of energy impact on the product to finally obtain the product, wherein the waste battery electrode material powder is lithium iron phosphate, ternary materials, graphite and the like.
4. The method for regenerating the electrode material of the lithium ion battery according to claim 3, wherein the quality of the regenerated electrode material product is determined according to the size of the releasable energy of the device, 100mg of the waste battery electrode material can be completely reduced by the energy within 1200J, and energy regulation and control can be performed according to different requirements of required products.
5. The method for recycling lithium ion battery electrode material of claim 3, wherein the multiple energy strikes on the product are performed after the material is placed in the device, and the capacitor charging and discharging processes are performed multiple times.
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| CN113003567A (en) * | 2021-05-06 | 2021-06-22 | 哈尔滨工程大学 | Device and method for reducing graphene oxide |
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