CN113346157A - Discharging and hydrogen producing integrated system and method for waste lithium ion battery - Google Patents

Abstract

The invention discloses a discharge and hydrogen production integrated system and a method for waste lithium ion batteries, wherein the integrated system comprises a power supply, an electrolytic cell, a controller, a battery appearance detection device and a battery charge and discharge performance test device which are assembled by a plurality of waste lithium ion battery monomers, the power supply is connected with the electrolytic cell to provide electric energy required by electrolytic reaction for the electrolytic cell, the residual electric quantity of a retired battery is effectively utilized through a hydrogen production technology by electrolysis, the retired battery after full discharge can directly enter a recycling disassembly step, and the residual electric energy is utilized while the discharge step is omitted.

Description

Discharging and hydrogen producing integrated system and method for waste lithium ion battery

Technical Field

The invention belongs to the field of waste battery recovery, and relates to a discharge and hydrogen production integrated system and method for a waste lithium ion battery.

Background

The number of retired batteries increases dramatically with the increase in battery usage. The problems of environmental pollution to a certain extent are caused by anode and cathode materials, electrolyte and other substances of the retired battery, and meanwhile, the retired battery still contains a certain amount of valuable metals, so the waste battery needs to be recycled. Since the waste battery usually contains a certain residual capacity, the discharge treatment is firstly needed in the traditional recovery process. The current discharge process is brine discharge, and this way not only produces a large amount of high-salt discharge waste water, but also wastes the remaining energy in the battery. The method should adopt certain means to replace the brine discharge process and realize the high-value utilization of the residual energy of the battery.

Hydrogen energy is one of new energy sources, is a green energy source which is developed in response to new energy sources, and the key for developing and storing hydrogen is the development of green hydrogen. The simple and pollution-free method for producing hydrogen by electrolyzing water is a widely applied and mature method, but the further application of the method is limited by the large power consumption of the method. The problem of large power consumption in hydrogen production by water electrolysis needs to be solved.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a discharge and hydrogen production integrated system and method for a waste lithium ion battery, which are safe, environment-friendly and high in energy recovery efficiency, and solves the problems of waste water discharge and energy waste in the traditional discharge process of the battery and large energy consumption in the hydrogen production method by electrolysis.

In order to achieve the purpose, the invention adopts the following technical scheme:

a waste lithium ion battery discharging and hydrogen producing integrated system comprises a power supply, an electrolytic cell, a controller, a battery appearance detection device and a battery charging and discharging performance testing device;

the power supply is formed by assembling a plurality of waste lithium ion battery monomers with better consistency obtained by screening, the power supply is connected with the electrolytic cell to provide electric energy required by electrolytic reaction for the electrolytic cell, the battery appearance detection device and the battery charge and discharge performance test device are respectively used for detecting the appearance and the voltage of the battery, and the controller is connected with the power supply, the battery appearance detection device and the battery charge and discharge performance test device to control the operation of the electrolytic cell by judging the battery state;

the electrolytic cell is respectively connected with a hydrogen storage tank and an oxygen storage tank which are used for collecting hydrogen and oxygen obtained by electrolysis, and a hydrogen purification device and an oxygen purification device are respectively arranged on pipelines connecting the hydrogen storage tank and the oxygen storage tank with the electrolytic cell.

Further, install hydrogen pressure sensor and oxygen pressure sensor on hydrogen holding vessel and the oxygen holding vessel respectively, hydrogen pressure sensor and oxygen pressure sensor all link to each other with the controller.

Further, the hydrogen purification device and the oxygen purification device both comprise a cooling device and a gas-liquid separation device.

Further, the hydrogen storage tank and the oxygen storage tank are respectively provided with an oxygen pressure regulator and a hydrogen pressure regulator, and are connected with oxygen and hydrogen output pipelines through the oxygen pressure regulator and the hydrogen pressure regulator.

Further, the electrolytic cell comprises a cathode chamber and an anode chamber, and the cathode chamber and the anode chamber are separated by a ceramic diaphragm.

Further, the ceramic diaphragm comprises a support body, and a lithium ion channel is formed in the support body.

The discharge and hydrogen production integrated method for the waste lithium ion battery comprises the following steps:

step 1), carrying out battery appearance detection and performance detection on the waste lithium ion batteries, screening out batteries with better quality, grouping the waste lithium ion batteries according to a detection result, and grouping the batteries with similar states into a group;

step 2), an integrated power supply is assembled by the batteries in the same group and is connected with an electrolytic cell, and the electrolytic cell carries out water electrolysis to convey separated hydrogen and oxygen to a hydrogen purification device and an oxygen purification device respectively for storage;

and 3) the controller regularly acquires a power supply pressure signal, a hydrogen pressure sensor signal and an oxygen pressure sensor signal of the power supply in the electrolytic reaction process, compares the acquired signals with a preset threshold value of the system, and controls to cut off the power supply and stop the electrolytic cell when the controller judges that the signals are abnormal.

Further, when the appearance of the battery is detected in the step 1), an industrial camera is used for collecting appearance data of the battery, batteries of different types and specifications are distinguished, and waste batteries with bulges and pole pieces falling off are removed.

Further, the battery is tested for the charge and discharge performance during the performance detection in the step 1), the capacity, the internal resistance and the charge and discharge voltage of the battery are obtained, the batteries are grouped according to the detection result, the difference between the internal resistances of the batteries in the same group is required to be not more than 5m omega, and the difference between the charge and discharge voltage is not more than 5 mV.

The invention has the following beneficial effects:

the discharge and hydrogen production integrated system for the waste lithium ion batteries comprises a power supply, an electrolytic cell, a controller, a battery appearance detection device and a battery charge and discharge performance testing device which are assembled by a plurality of waste lithium ion battery monomers, wherein the power supply is connected with the electrolytic cell to provide electric energy required by electrolytic reaction for the electrolytic cell, the residual electric quantity of the retired battery is effectively utilized through the hydrogen production technology by electrolysis, the retired battery after full discharge can directly enter the disassembly step of recovery, and the residual electric energy is utilized while the discharge step is omitted.

The voltage required by the traditional water electrolysis hydrogen production process is usually 1.8-2.0V, the lowest driving force is 1.23V, a cathode chamber and an anode chamber of the electrolytic cell are separated by a ceramic diaphragm, and an alkali-acid mixed electrolysis system successfully combines the low OER potential in an alkaline electrolyte solution and the high HER potential in an acidic electrolyte solution through a ceramic lithium ion exchange membrane. The minimum required voltage is lower than the theoretical value, the water electrolysis hydrogen production technology reduces the required driving force, can normally run under the driving force of the minimum voltage of 0.78V, and greatly reduces the electric energy consumption. The electrolytic cell is connected respectively and is used for collecting the hydrogen holding vessel and the oxygen holding vessel of electrolysis gained hydrogen and oxygen, can avoid hydrogen and oxygen to mix at the in-process of electrolysis water, provides the gas of being convenient for purification for follow-up technology, improves the stability of system operation.

The device is provided with a battery appearance detection device and a battery charging and discharging performance testing device which are respectively used for detecting the appearance and the voltage of a battery, the appearance and the performance of the waste battery are detected before working, a proper battery is selected as a power supply of an electrolytic cell according to a detection result, a controller is arranged, the controller is connected with the power supply, the battery appearance detection device and the battery charging and discharging performance testing device, the work of the electrolytic cell is controlled by judging the state of the battery, and the normal and efficient work of an electrolytic reaction is ensured.

Drawings

FIG. 1 is a schematic diagram of the system of the present invention;

FIG. 2 is a schematic diagram of the operation of the electrolytic cell of the present invention;

FIG. 3 is a schematic structural view of a ceramic lithium ion exchange membrane in an electrolytic cell;

in the figure: 1-a power supply; 2-an electrolytic cell; 3-a hydrogen purification unit; 4-an oxygen purification device; 5-a hydrogen storage tank; 6-oxygen storage tank; 7-a hydrogen pressure sensor; 8-an oxygen pressure sensor; 9-hydrogen pressure regulator; 10-oxygen pressure regulator; 11-a controller; 12-battery appearance detection means; 13-battery charge and discharge performance testing device; 14-a ceramic diaphragm; 15-a cathode chamber; 16-an anode chamber; 17-a lithium ion channel; 18-a support; a-hydrogen pressure sensor signal; b-oxygen pressure sensor signal; c-a power supply control signal; d-power supply pressure signal; e-a battery appearance data signal; f-battery charge and discharge performance data signal.

Detailed Description

The present invention will be explained in further detail with reference to examples.

As shown in fig. 1, the integrated system for discharging and producing hydrogen of waste lithium ion batteries of the present invention includes apower supply 1, an electrolytic cell 2, ahydrogen purification device 3, anoxygen purification device 4, ahydrogen storage tank 5, anoxygen storage tank 6, ahydrogen pressure sensor 7, anoxygen pressure sensor 8, ahydrogen pressure regulator 9, anoxygen pressure regulator 10, acontroller 11, a batteryappearance detection device 12, and a battery charging and dischargingperformance test device 13.

The batteryappearance detection device 12 comprises an industrial camera, waste batteries are placed on a conveyor belt one by one during operation, the industrial camera is used for collecting battery appearance data when the batteries pass through a scanner, and the data are transmitted to a computer for processing. The rejected residual batteries are transmitted to a battery charging and dischargingperformance testing device 13 to detect various data, and the data are processed and displayed by a computer.

The retired batteries are detected and screened to obtain battery combinations with good consistency, the screened batteries are assembled into an integrated power supply to be connected with an electrolytic cell, and the electrolytic cell respectively conveys separated hydrogen and oxygen to ahydrogen purification device 3 and anoxygen purification device 4. Thehydrogen purification device 3 and theoxygen purification device 4 are respectively connected with ahydrogen storage tank 5 and anoxygen storage tank 6, and pressure regulators are respectively arranged behind the storage tanks. Thecontroller 11 is connected to thepower supply 1 and thehydrogen pressure sensor 7 and theoxygen pressure sensor 8 which are respectively arranged on the hydrogen storage tank and the oxygen storage tank.

Thecontroller 11 is connected with thepower supply 1 to obtain a power supply voltage signal d, thecontroller 11 feeds back a power supply control signal c to thepower supply 1, the power supply is provided with a relay control loop, and the power supply is controlled to be connected with the electrolytic cell 2 through a power supply relay; the hydrogen and oxygen pressure sensors are both connected with the controller, and thecontroller 11 obtains hydrogen and oxygen pressure signals, namely a hydrogen pressure sensor signal a and an oxygen pressure sensor signal b; the battery appearance detection means 12 provides a battery appearance data signal e to thecontroller 11; the battery charge and dischargeperformance testing device 13 provides a battery charge and discharge performance data signal f to thecontroller 11.

Thehydrogen purification device 3 and theoxygen purification device 4 each include a cooling device, a gas-liquid separation device, and the like. Hydrogen is separated from water vapor through a hydrogen purification device, and the obtained high-purity hydrogen is transported to ahydrogen storage tank 5 through a gas conveying pipeline; the oxygen is separated from the water vapor by the oxygen purification device, and the obtained high-purity oxygen is transported to theoxygen storage tank 6 by the gas transportation pipeline.

The hydrogen and oxygen pressure regulators can deliver gas at a constant pressure and volume to regulate the outlet pressure of hydrogen and oxygen. Gas pressure regulators are used in processes requiring precise, consistent control of pressure to maintain gas purity in a delivery system.

The controller takes a microcomputer system as a core to carry out signal acquisition and calculation, analysis and decision of a countermeasure and issue a control instruction. The controller provides stable power supply for the hydrogen and oxygen pressure sensors, and provides working parameters and working conditions with reference values for the whole system. The controller can realize automatic control, so that danger in system work can be avoided to a great extent, and meanwhile, an operator can carry out remote monitoring to improve the work efficiency.

When a, b and d received by the controller are all abnormal, the system operates normally; when an abnormal signal occurs, the control method of the controller for the whole system comprises the following three conditions:

1) signal a is abnormal

In order to ensure the safe operation of the system, when the pressure of the hydrogen storage tank is greater than or equal to the preset maximum pressure of the storage tank, the hydrogen pressure sensor signal a received by the hydrogen pressure sensor is controlled. At the moment, the controller immediately sends a power control signal c to the power supply, and the power supply is cut off to stop the work of the electrolytic cell. And the operator can replace the hydrogen storage tank in time after finding abnormality through remote monitoring.

2) Signal b abnormal

In order to ensure the safe operation of the system, when the pressure of the oxygen storage tank is greater than or equal to the preset maximum pressure of the storage tank, the control receives the oxygen pressure sensor signal b of the oxygen pressure sensor. At the moment, the controller immediately sends a power control signal c to the power supply, and the power supply is cut off to stop the work of the electrolytic cell. And an operator can timely replace the oxygen storage tank after finding abnormality through remote monitoring.

3) Signal d abnormal

The integrated power supply assembled by the retired batteries gradually reduces the residual energy of the batteries in the process of discharging and producing hydrogen, and when the power supply voltage is lower than the minimum voltage required by the electrolytic cell to work, the controller receives a power supply pressure signal d. At the moment, the controller immediately sends a power control signal c to the power supply, and the power supply is cut off to stop the work of the electrolytic cell. And an operator can timely replace the power supply after finding abnormality through remote monitoring.

Fig. 2 is a working schematic diagram of an electrolytic cell, and in the water electrolysis hydrogen production system, the electrolytic cell adopts an acid-base mixed water electrolysis technology using a ceramic lithium ion exchange membrane as a diaphragm. The electrolytic cell is divided into acathode chamber 15 and ananode chamber 16 with aceramic diaphragm 14 as a boundary. As shown in fig. 3, theceramic membrane 14 haslithium ion channels 17 for selectively passing lithium ions, and thesupport 18 ensures that the ceramic membrane does not collapse. The water electrolysis technology can be driven by the waste lithium ion battery to generate hydrogen evolution reaction without generating hydrogen and oxygen mixing phenomenon.

In the water electrolysis hydrogen production system, the power supply is formed by assembling a plurality of battery monomers which are obtained through screening and have better consistency. In order to avoid the technical and economic problems caused by battery welding, the existing battery rack can be adopted to directly insert the battery monomers into the preset battery cavities respectively, and the integrated battery module is assembled through operations of uniform placement, wire arrangement and the like. The battery rack has the advantages that the battery rack is convenient to replace in the using process and simultaneously provides sufficient voltage for the electrolytic cell. The battery pack provides a voltage of approximately 1.0-7.0V for the electrolytic cell; the battery pack is a high-frequency direct-current power supply.

The power supply is formed by inserting a plurality of screened and classified battery cores into a battery rack. Considering stability and security in the use process of the retired battery, the waste battery is divided into different grades according to a certain standard so as to be combined into a battery module with good consistency, and the battery screening process is as follows:

firstly, battery appearance detection is carried out, and the controller analyzes appearance basic data of the battery to carry out primary screening after receiving a signal e;

and then, testing the charging and discharging performance of the battery, analyzing the charging and discharging performance data signal f of the battery according to the capacity, the internal resistance and the charging and discharging voltage of the battery by using the controller, and secondarily screening and grouping the waste batteries. The screened batteries in the same group are used in the same battery rack, so that the power supply efficiency and stability of the power supply can be improved.

The following concrete implementation cases illustrate the discharge and hydrogen production integrated system method of the waste lithium ion battery, which comprises the following steps:

firstly, detecting and screening retired batteries to obtain battery combinations with good consistency, assembling the screened batteries into an integrated power supply to be connected with an electrolytic cell, and respectively conveying separated hydrogen and oxygen to a hydrogen purification device and an oxygen purification device by the electrolytic cell;

appearance detection is carried out on the retired batteries one by one during screening, and an industrial camera can be used for collecting appearance data of the batteries. The method has the advantages that batteries of different types and specifications are distinguished, and waste batteries with the phenomena of bulging, pole piece falling and the like are removed. The primarily screened batteries are subjected to battery charging and discharging performance tests, the batteries can be divided into 80-60%, 60-40% and 40-20% according to the battery capacity, and the batteries with the capacity lower than 20% are directly rejected; the batteries used for the same module require that the difference of internal resistance is not more than 5m omega, and the difference of charging and discharging voltage is not more than 5 mV. And the screened batteries are grouped for standby, the batteries in the same group are inserted into a battery rack to form a series circuit for supplying power for hydrogen production, and the batteries in the battery rack are replaced when the voltage is lower than 0.78V.

The power supply provides a low voltage driving force for the electrolytic reaction, with the lowest voltage at which the electrolytic reaction can occur being 0.78V. Hydrogen and oxygen generated in the electrolytic cell are respectively conveyed to a hydrogen purification device and an oxygen purification device from pipelines, and high-purity hydrogen and oxygen are obtained through certain cooling and gas-liquid separation and then respectively enter a hydrogen storage tank and an oxygen storage tank. The design pressure of the hydrogen storage tank is 35MPa, and the maximum preset pressure is 45 MPa. The design pressure of the oxygen storage tank is 10MPa, and the maximum preset pressure is 15 MPa. The pressure regulator can stabilize the outlet pressure of the hydrogen and oxygen generated by the process at a certain value.

Secondly, the controller obtains a power supply pressure signal d, and feeds back a power supply control signal c to the power supply; the hydrogen and oxygen pressure sensors are connected with a controller, and the controller obtains pressure signals a and b; when the pressure signals a and b received by the controller are lower than the preset highest pressure and the voltage signal d is higher than the minimum voltage required by work, the system normally operates; when an abnormal signal occurs, the control method of the controller for the whole system comprises the following three conditions:

1) signal a is abnormal

In order to ensure the safe operation of the system, when the pressure of the hydrogen storage tank is greater than or equal to the preset maximum pressure of the storage tank by 45MPa, the hydrogen pressure sensor signal a received by the hydrogen pressure sensor is controlled. At the moment, the controller immediately sends a feedback hydrogen pressure sensor signal c to the power supply, the power supply is cut off, and the electrolytic cell stops working. And the operator can replace the hydrogen storage tank in time after finding abnormality through remote monitoring.

2) Signal b abnormal

In order to ensure the safe operation of the system, when the pressure of the oxygen storage tank is greater than or equal to the preset maximum pressure 15MPa of the storage tank, the oxygen pressure sensor signal b of the oxygen pressure sensor is controlled and received. At the moment, the controller immediately sends a power control signal c to the power supply, and the power supply is cut off to stop the work of the electrolytic cell. And an operator can timely replace the oxygen storage tank after finding abnormality through remote monitoring.

3) Signal d abnormal

The integrated power supply assembled by the retired batteries gradually reduces the residual energy of the batteries in the process of discharging to produce hydrogen, and when the power supply voltage is lower than the minimum voltage 0.78V required by the work of the electrolytic cell, the controller receives a power supply pressure signal d. At the moment, the controller immediately sends a power control signal c to the power supply, and the power supply is cut off to stop the work of the electrolytic cell. And an operator can timely replace the power supply after finding abnormality through remote monitoring.

The specific case that the retired battery is used for producing hydrogen by electrolyzing water shows that the process provided by the invention overcomes the defect of large electric energy consumption in the traditional process, and can utilize the residual electric energy in the waste battery in a high-value manner. The hydrogen and oxygen which are economical and environment-friendly are produced under the condition of lower cost, and the development of the technology for producing hydrogen by electrolyzing water is promoted.

Claims (9)

1. The utility model provides a waste lithium ion battery discharges and produces hydrogen integration system which characterized in that: the device comprises a power supply (1), an electrolytic cell (2), a controller (11), a battery appearance detection device (12) and a battery charging and discharging performance test device (13);

the power supply (1) is formed by assembling a plurality of waste lithium ion battery monomers with good consistency obtained through screening, the power supply (1) is connected with the electrolytic cell (2) to provide electric energy required by electrolytic reaction for the electrolytic cell, the battery appearance detection device (12) and the battery charge and discharge performance test device (13) are respectively used for detecting the appearance and the voltage of the battery, and the controller (11) is connected with the power supply (1), the battery appearance detection device (12) and the battery charge and discharge performance test device (13) to control the operation of the electrolytic cell by judging the battery state;

the electrolytic cell (2) is respectively connected with a hydrogen storage tank (5) and an oxygen storage tank (6) which are used for collecting hydrogen and oxygen obtained by electrolysis, and a hydrogen purification device (3) and an oxygen purification device (4) are respectively arranged on pipelines which are connected with the electrolytic cell (2) by the hydrogen storage tank (5) and the oxygen storage tank (6).

2. The integrated system for discharging and hydrogen production of waste lithium ion batteries according to claim 1, characterized in that: install hydrogen pressure sensor (7) and oxygen pressure sensor (8) on hydrogen holding vessel (5) and oxygen holding vessel (6) respectively, hydrogen pressure sensor (7) and oxygen pressure sensor (8) all link to each other with controller (11).

3. The integrated system for discharging and hydrogen production of waste lithium ion batteries according to claim 2, characterized in that: the hydrogen purification device (3) and the oxygen purification device (4) both comprise a cooling device and a gas-liquid separation device.

4. The integrated system for discharging and producing hydrogen of the waste lithium ion battery according to any one of claims 1 to 3, wherein: the hydrogen storage tank (5) and the oxygen storage tank (6) are respectively provided with an oxygen pressure regulator (10) and a hydrogen pressure regulator (9), and oxygen and hydrogen output pipelines are connected through the oxygen pressure regulator (10) and the hydrogen pressure regulator (9).

5. The integrated system for discharging and hydrogen production of waste lithium ion batteries according to claim 4, characterized in that: the cell comprises a cathode chamber (15) and an anode chamber (16), the cathode chamber (15) and the anode chamber (16) being separated by a ceramic diaphragm (14).

6. The integrated system for discharging and hydrogen production of waste lithium ion batteries according to claim 5, characterized in that: the ceramic diaphragm (14) comprises a support body (18), and a lithium ion channel (17) is formed in the support body (18).

7. The discharge and hydrogen production integrated method for the waste lithium ion battery based on the system of claim 6 is characterized by comprising the following steps:

step 1), carrying out battery appearance detection and performance detection on the waste lithium ion batteries, screening out batteries with better quality, grouping the waste lithium ion batteries according to a detection result, and grouping the batteries with similar states into a group;

step 2), an integrated power supply is assembled by the batteries in the same group and is connected with an electrolytic cell, and the electrolytic cell carries out water electrolysis to convey separated hydrogen and oxygen to a hydrogen purification device (3) and an oxygen purification device (4) respectively and store the hydrogen and oxygen;

and 3) in the electrolytic reaction process, the controller (11) acquires a power supply pressure signal (d), a hydrogen pressure sensor signal (a) and an oxygen pressure sensor signal (b) of the power supply (1) at regular time, the controller (11) compares the acquired signals with a system preset threshold value, and the controller controls to cut off the power supply and stop the electrolytic cell when the judgment that the signals are abnormal is made.

8. The discharge and hydrogen production integrated method for the waste lithium ion battery based on claim 7 is characterized in that: during the detection of the battery appearance in the step 1), an industrial camera is adopted to collect battery appearance data, batteries of different types and specifications are distinguished, and waste batteries with bulges and pole piece falling are removed.

9. The discharge and hydrogen production integrated method for the waste lithium ion battery based on claim 7 is characterized in that: and (2) testing the charging and discharging performance of the battery in the step 1) during performance detection to obtain the capacity, the internal resistance and the charging and discharging voltage of the battery, grouping the batteries according to the detection result, wherein the difference between the internal resistances of the batteries in the same group is required to be not more than 5m omega, and the difference between the charging and discharging voltage is not more than 5 mV.

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