A thermal regeneration electrochemical waste heat power generation system combined with a thermal battery

Abstract

The application relates to the technical field of thermoelectric chemical thermoelectric power generation, in particular to a kind of thermally regenerated electrochemical cycle waste heat power generation system combined with thermal primary cell, solve the existing in conventional TREC system, usually adopt waste heat direct heating regenerative electrochemical cell, due to the existence of certain temperature difference between heat source and cold source and TREC, will produce heat loss and lead to incomplete waste heat utilization and there is partial energy waste, thereby to a certain extent limit the power generation power problem, including temperature processing device, TGC module and TREC module, the temperature processing device includes waste heat collection device and cooling device, one side of the waste heat collection device and cooling device is installed with TGC module. The application utilizes the space temperature difference between waste heat collection system and thermal regenerative electrochemical cell to realize the cyclic power generation of thermal primary cell, couples and integrates thermal regenerative electrochemical system and thermal primary cell system, realizes more efficient utilization of low-grade waste heat, and improves thermoelectric power generation efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of thermoelectrochemical temperature difference power generation, and in particular to a heat regeneration electrochemical cycle waste heat power generation system combined with a thermoelectric cell. Background Art

[0002] A thermal regenerative electrochemical cycle (TREC) is an electrochemical cycle system that uses time-dependent temperature differences to convert heat into electricity. It includes four processes: heating, charging, cooling, and discharging. A thermogenic cell (TGC) is a battery driven by spatial temperature differences. Unlike the TREC operating mode, a thermogenic cell creates a temperature gradient by applying different temperatures to two symmetrical electrodes, achieving a potential difference based on diffusion effects and electrochemical redox reactions. The oxidation reaction releases electrons to one electrode, while the reduction reaction absorbs electrons from the other. The electrons flowing between the two electrodes and the ions moving in the battery form a closed loop, generating continuous electrical energy.

[0003] In existing conventional TREC systems, waste heat is usually used to directly heat regenerative electrochemical cells. Due to a certain temperature difference between the heat source and the cold source and the TREC, heat loss will occur, resulting in incomplete utilization of waste heat and some energy waste, which to a certain extent limits the power generation capacity. Therefore, it does not meet existing needs. In this regard, we propose a heat regeneration electrochemical cycle waste heat power generation system combined with thermogenic cells. Summary of the Invention

[0004] The object of the present invention is to provide a heat regeneration electrochemical cycle waste heat power generation system combined with a thermoelectric cell, so as to solve the problem raised in the above background art that in the conventional TREC system, waste heat is usually used to directly heat the regenerative electrochemical cell. Due to a certain temperature difference between the heat source and the cold source and the TREC, heat loss will occur, resulting in incomplete utilization of waste heat and partial energy waste, thereby limiting the power generation capacity to a certain extent.

[0005] To achieve the above objectives, the present invention provides the following technical solutions: a thermoelectrochemical waste heat power generation system in combination with a thermoelectric cell, comprising a temperature treatment device, a TGC module, and a TREC module; the temperature treatment device comprises a waste heat collection device and a cooling device; a TGC module is mounted on one side of the waste heat collection device and the cooling device; a TREC module is mounted on one side of the TGC module; the waste heat collection device, the TGC module, the TREC module, and the cooling device are electrically connected via a circuit board;

[0006] The TREC module includes a TREC battery pack and a first heat exchange component, wherein the first heat exchange component is arranged outside the TREC battery pack, the TREC battery pack includes a battery positive electrode, a battery negative electrode, a positive electrode electrolyte, a negative electrode electrolyte and an ion exchange membrane, the ion exchange membrane is arranged between the battery positive electrode and the battery negative electrode, the positive electrode electrolyte is filled between the battery positive electrode and the ion exchange membrane, and the negative electrode electrolyte is filled between the battery negative electrode and the ion exchange membrane;

[0007] The TGC module includes a TGC and a second heat exchange component, wherein the second heat exchange component is arranged outside the TGC. The TGC includes a battery cold electrode, a battery hot electrode and an electrolyte, and the electrolyte is filled between the battery cold electrode and the battery hot electrode;

[0008] The waste heat collection device includes a heat absorbing medium, which is a common heat-conducting fluid such as water or thermal oil; the cooling device includes a cooling medium, which is water or air;

[0009] The waste heat collection device and the cooling device also include a heat transfer device, which is one or more packaged metal heat conducting sheets, heat conducting pipes or heat conducting plates.

[0010] Preferably, the first heat exchange component and the second heat exchange component are both composed of heat exchange plates and heat storage medium, and the heat storage medium is filled into the interior of the heat exchange plates.

[0011] Preferably, the waste heat collection device absorbs low-grade heat such as industrial waste heat, flue gas waste heat, data center waste heat, or absorbs solar heat through a heat-absorbing medium in a contact manner, and the waste heat collection device conducts the heat to the inner side of the second heat exchange component and the first heat exchange component in turn.

[0012] Preferably, the first heat exchange component can maintain the TREC module in a high temperature state after absorbing heat, and the second heat exchange component can maintain the hot and cold electrodes in the TGC module in a temperature difference state after absorbing heat.

[0013] Preferably, the waste heat collection device and the cooling device are connected in sequence through a TGC module and a TREC module, and the heat in the waste heat collection device passes through the TGC module, the TREC module and the cooling device in sequence, and thermal conductive glue is coated between the waste heat collection device, the TGC module, the TREC module and the cooling device.

[0014] Preferably, the models of the TGC modules are divided into P type, N type and P / N alternating type.

[0015] A power generation cycle method of a thermoelectrochemical waste heat power generation system combined with a thermoelectric cell, comprising the following steps:

[0016] S1: First, the waste heat collection device absorbs low-grade waste heat and transfers the heat to the TGC module. The heat source is 70°C, and then transfers it to the TREC module, causing its overall temperature to rise to 60°C. At this time, the temperature difference between the waste heat collection device and the TREC module can be utilized by the TGC module. Since the positive electrode material of the TREC module has a negative temperature coefficient and the negative electrode material has a positive temperature coefficient, the open-circuit voltage of the TREC module decreases. The TGC module reaches a high voltage under the action of the temperature difference and enters the continuous operation mode. The TREC module is charged at a low voltage at a high temperature and absorbs heat due to entropy increase during the electrochemical reaction.

[0017] S2: After a period of time, the waste heat collection device is disconnected, and the cold source is 20°C. At this time, the overall temperature of the TREC module drops to the initial state of 30°C under the action of the cooling device, and its open circuit voltage increases. At this time, the temperature difference between the TREC module and the cooling device can be reused by the TGC module. Finally, the TGC module is connected to an external circuit, so that the TGC in the TGC module is discharged to 0V in a short time, and the current rises linearly to the maximum value. This is because during the discharge process, electrons flow from the hot side to the cold side through the external circuit, resulting in a decrease in the internal electrostatic field, thereby reducing the battery voltage. The TREC module completes discharge at a high voltage at a low temperature, the battery entropy decreases and releases heat to the environment, and returns to the original discharge state. Since the charging voltage is lower than the discharging voltage, the charge and discharge energy difference is extracted as the net work W. After completing this cycle, the charge and discharge cycle is repeated many times;

[0018] S3: Since TGC modules are divided into three types: P-type, N-type and P / N alternating types, when the TREC module uses the P-type TGC module for waste heat power generation, in the heating stage, the waste heat is absorbed by the waste heat collection device and then transferred to the P-type TGC module, and then transferred to the TREC module, causing its overall temperature to rise to 60°C. At this time, the temperature difference between the hot and cold sides of the P-type TGC module is 10K. In the charging stage, the P-type TGC module reaches a high near-saturation voltage based on the Soret effect and thermoelectric effect under the action of the temperature difference. The TREC module charges at a low voltage at high temperature. In the cooling stage, the waste heat collection device is disconnected, and the overall temperature of the TREC module drops to the initial state of 30°C under the action of the cooling device. At this time, the temperature difference between the hot and cold sides of the P-type TGC module is 10K. In the discharging stage, the P-type TGC module is connected to an external circuit, and the battery discharges to 0V in a short time. The TREC module completes the discharge at a high voltage at a low temperature.

[0019] S4: When the TREC module uses the N-type TGC module to generate waste heat, in the heating stage, the waste heat is absorbed by the waste heat collection device and then transferred to the N-type TGC module, and then to the TREC module, causing its overall temperature to rise to 60°C. At this time, the temperature difference between the hot and cold sides of the N-type TGC module is 10K. At the same time, the hot end of the N-type TGC module is connected to the external load in the circuit, and the current passes through the external load to balance the voltage generated by the ions. In the charging stage, the N-type TGC module reaches a high voltage based on cooperative coordination and hydration under the action of the temperature difference. Then, the TREC module is charged at a low voltage at high temperature. In the cooling stage, the waste heat collection device and the external load of the N-type TGC module are disconnected. Under the action of the cooling device, the overall temperature of the TREC module drops to the initial state of 30°C. At this time, the temperature difference between the hot and cold sides of the N-type TGC module is 10K. In the discharging stage, the N-type TGC module is reconnected to the external load, the battery is discharged to 0V in a short time, and the TREC module completes the discharge at a high voltage at a low temperature.

[0020] S5: When the TREC module uses the P / N alternating TGC module for waste heat power generation, in the heating stage, the waste heat is absorbed by the waste heat collection device and then transferred to the P / N alternating TGC module, and then transferred to the TREC module to raise its overall temperature to 60°C. At this time, the temperature difference between the hot side and the cold side of the P / N alternating TGC module is 10K, and the hot side temperature is higher than the gelation transition temperature, which shows a P-type. In the charging stage, the P-type TGC module, under the action of temperature difference, based on the gelation of cellulose in the electrolyte and ion induction The complexation effect reaches a high voltage. Secondly, the TREC module is charged at a low voltage at a high temperature. In the cooling stage, the waste heat collection device is disconnected. Under the action of the cooling device, the overall temperature of the TREC module drops to the initial state of 30 ° C. At this time, the temperature difference between the hot and cold sides of the P / N alternating TGC module is 10K, and the hot side temperature drops below the gelation transition temperature and turns into N type. In the discharge stage, the N-type TGC module is connected to the external circuit, and the battery is discharged to 0V in a short time. The TREC module completes the discharge at a high voltage at a low temperature.

[0021] Preferably, a heat source and a cold source are respectively provided on the outside of the waste heat collection device and the cooling device. The power generated by the TGC module using the temperature difference between the heat source and the TREC module is recorded as W1, the power generated by the TREC module using the temperature difference is recorded as W2, and the power generated by the TGC module using the temperature difference between the cold source and the TREC module is recorded as W3. The heat amount of the heat source is recorded as Q.

[0022] The calculation formula for the average charge and discharge voltage difference obtained by the TREC module is:

[0023]

[0024] The formula for calculating the power generation of the TREC module in one hour is:

[0025]

[0026] The maximum power generation efficiency calculation formula of the TGC module is:

[0027]

[0028] in The thermoelectric figure of merit, that is, the calculation formula for the power generation W1 and W3 corresponding to the thermoelectric coefficient of the material under different working conditions is:

[0029] W1=η max1 Q;

[0030] W3=η max2 Q;

[0031] The calculation formula for the improvement of the power generation efficiency of the TREC module is:

[0032]

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] The present invention arranges a thermoelectric cell module between a waste heat collection device, a cooling device and a heat regeneration electrochemical cell module. Based on the original heat regeneration electrochemical cell generating power through time temperature difference cycle, the present invention utilizes the spatial temperature difference between the waste heat collection system and the heat regeneration electrochemical cell to realize the cyclic power generation of the thermoelectric cell. The heat regeneration electrochemical system and the thermoelectric cell system are coupled and integrated, thereby achieving more efficient utilization of low-grade waste heat and improving the efficiency of thermoelectric power generation. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a schematic structural diagram of the present invention as a whole;

[0036] Figure 2 Schematic diagram of the structure of the TREC module of the present invention;

[0037] Figure 3 Schematic diagram of the structure of the TGC module of the present invention;

[0038] Figure 4 Schematic diagram of the TGC module of the present invention;

[0039] Figure 5 This is a schematic diagram of the operation of the P-type TGC module of the present invention:

[0040] Figure 6 Schematic diagram of the operation of the N-type TGC module of the present invention;

[0041] Figure 7 Schematic diagram of the operation of the P / N alternating TGC module of the present invention.

[0042] In the figure: 1. Waste heat collection device; 2. TGC module; 3. TREC module; 4. Cooling device. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0044] See also Figures 1 to 4 , the present invention provides a first embodiment: a thermoelectrochemical waste heat power generation system combined with a thermoelectric cell, comprising a temperature treatment device, a TGC module 2 and a TREC module 3, the temperature treatment device comprising a waste heat collection device 1 and a cooling device 4, the TGC module 2 is installed on one side of the waste heat collection device 1 and the cooling device 4, and the TREC module 3 is installed on one side of the TGC module 2, the waste heat collection device 1, the TGC module 2, the TREC module 3 and the cooling device 4 are electrically connected with a circuit board, the waste heat collection device 1 and the cooling device 4 are connected in turn through the TGC module 2 and the TREC module 3, the heat in the waste heat collection device 1 passes through the TGC module 2, the TREC module 3 and the cooling device 4 in turn, and thermal conductive glue is coated between the waste heat collection device 1, the TGC module 2, the TREC module 3 and the cooling device 4, and the thermal conductive glue can quickly transfer the heat inside the waste heat collection device 1, the TGC module 2, the TREC module 3 and the cooling device 4.

[0045] See also Figure 2 The TREC module 3 includes a TREC battery pack and a first heat exchange component. The first heat exchange component is arranged on the outside of the TREC battery pack. The TREC battery pack includes a battery positive electrode, a battery negative electrode, a positive electrode electrolyte, a negative electrode electrolyte and an ion exchange membrane. The ion exchange membrane is arranged between the battery positive electrode and the battery negative electrode. The positive electrode electrolyte is filled between the battery positive electrode and the ion exchange membrane, and the negative electrode electrolyte is filled between the battery negative electrode and the ion exchange membrane. Electrons can be exchanged through the ion exchange membrane.

[0046] See also Figure 3 and Figure 4 The TGC module 2 includes a TGC and a second heat exchange component. The second heat exchange component is arranged on the outside of the TGC. The TGC includes a battery cold electrode, a battery hot electrode and an electrolyte. The electrolyte is filled between the battery cold electrode and the battery hot electrode. The TGC module 2 can generate electricity by generating a temperature difference between the battery cold electrode and the battery hot electrode.

[0047] See also Figure 1The waste heat collection device 1 includes a heat absorbing medium, which is a common heat-conducting fluid such as water or thermal oil. The waste heat collection device 1 absorbs low-grade heat such as industrial waste heat, flue gas waste heat, data center waste heat, or solar heat through the heat absorbing medium in a contact manner. The waste heat collection device 1 conducts the heat to the inner side of the second heat exchange component and the first heat exchange component in sequence. The heat from the heat source can be transferred to the TGC module 2 through the waste heat collection device 1.

[0048] The cooling device 4 includes a cooling medium, which is water or air. The waste heat collection device 1 and the cooling device 4 also include a heat exchanger, which is one or more packaged metal heat conducting sheets, heat conducting tubes or heat conducting plates. The first heat exchange component and the second heat exchange component are both composed of heat exchange plates and heat storage medium. The heat storage medium is filled into the interior of the heat exchange plates. After the first heat exchange component absorbs heat, it can maintain the TREC module 3 in a high temperature state. After the second heat exchange component absorbs heat, it can maintain the hot and cold electrodes in the TGC module 2 in a temperature difference state. The cooling device 4 can use the cold source to cool the TGC module 2.

[0049] See also Figure 4 ,The models of TGC module 2 are divided into P type, N type and P / N alternating type.

[0050] The overall heat transfer process starts from the heat source, and is transferred in sequence through the waste heat collection device 1, the P-type TGC module 2, the TREC module 3, the P-type TGC module 2 and the cooling device 4, and is finally discharged to the environment.

[0051] See also Figures 5 to 7 A power generation cycle method of a thermoelectrochemical waste heat power generation system combined with a thermoelectric cell comprises the following steps:

[0052] S1: First, the waste heat collection device 1 absorbs low-grade waste heat and transfers the heat to the TGC module 2. The heat source is 70°C, and then transfers it to the TREC module 3, causing its overall temperature to rise to 60°C. At this time, the temperature difference between the waste heat collection device 1 and the TREC module 3 can be utilized by the TGC module 2. Since the positive electrode material of the TREC module 3 has a negative temperature coefficient and the negative electrode material has a positive temperature coefficient, the open circuit voltage of the TREC module 3 decreases. The TGC module 2 reaches a high voltage under the action of the temperature difference and enters the continuous operation mode. The TREC module 3 is charged at a low voltage at a high temperature and absorbs heat due to entropy increase during the electrochemical reaction.

[0053] S2: After a period of time, the waste heat collection device is disconnected, and the cold source is 20°C. At this time, the overall temperature of the TREC module 3 drops to the initial state of 30°C under the action of the cooling device 4, and its open circuit voltage increases. At this time, the temperature difference between the TREC module 3 and the cooling device 4 can be reused by the TGC module 2. Finally, the TGC module 2 is connected to the external circuit, so that the TGC in the TGC module 2 is discharged to 0V in a short time, and the current rises linearly to the maximum value. This is because during the discharge process, electrons flow from the hot side to the cold side through the external circuit, resulting in a decrease in the internal electrostatic field, thereby reducing the battery voltage. The TREC module 3 completes the discharge at a high voltage at a low temperature, the battery entropy decreases and releases heat to the environment, and returns to the original discharge state. Since the charging voltage is lower than the discharging voltage, the charge and discharge energy difference is extracted as the net work W. After completing this cycle, the charge and discharge cycle is repeated many times;

[0054] S3: Since the TGC module 2 is divided into three types, namely P-type, N-type and P / N alternating type, when the TREC module 3 uses the P-type TGC module 2 to generate waste heat, in the heating stage, the waste heat is absorbed by the waste heat collection device 1 and transferred to the P-type TGC module 2, and then transferred to the TREC module 3, causing its overall temperature to rise to 60°C. At this time, the temperature difference between the hot side and the cold side of the P-type TGC module 2 is 10K. In the charging stage, the P-type TGC module 2 reaches a high near-saturation voltage based on the Soret effect and the thermoelectric effect under the action of the temperature difference, and the TREC module 3 is charged at a low voltage at high temperature. In the cooling stage, the waste heat collection device 1 is disconnected, and the overall temperature of the TREC module 3 drops to the initial state of 30°C under the action of the cooling device 4. At this time, the temperature difference between the hot side and the cold side of the P-type TGC module 2 is 10K. In the discharging stage, the P-type TGC module 2 is connected to the external circuit, and the battery is discharged to 0V in a short time. The TREC module 3 completes the discharge at a high voltage at a low temperature.

[0055] S4: When the TREC module 3 uses the N-type TGC module 2 to generate waste heat, in the heating stage, the waste heat is absorbed by the waste heat collection device 1 and then transferred to the N-type TGC module 2, and then to the TREC module 3, causing the overall temperature to rise to 60°C. At this time, the temperature difference between the hot side and the cold side of the N-type TGC module 2 is 10K. At the same time, the hot end of the N-type TGC module 2 is connected to the external load in the circuit, and the current passes through the external load to balance the voltage generated by the ions. In the charging stage, the N-type TGC module 2 is under the action of the temperature difference. Based on The coordinated coordination and hydration achieve high voltage. Then, the TREC module 3 is charged at low voltage at high temperature. In the cooling stage, the waste heat collection device 1 and the external load of the N-type TGC module 2 are disconnected. The overall temperature of the TREC module 3 drops to the initial state of 30°C under the action of the cooling device 4. At this time, the temperature difference between the hot side and the cold side of the N-type TGC module 2 is 10K. In the discharge stage, the N-type TGC module 2 is reconnected to the external load. The battery is discharged to 0V in a short time. The TREC module 3 completes the discharge at high voltage at low temperature.

[0056] S5: When the TREC module 3 uses the P / N alternating TGC module 2 to generate waste heat, in the heating stage, the waste heat is absorbed by the waste heat collection device 1 and then transferred to the P / N alternating TGC module 2, and then transferred to the TREC module 3 to raise its overall temperature to 60°C. At this time, the temperature difference between the hot side and the cold side of the P / N alternating TGC module 2 is 10K, and the hot side temperature is higher than the gelation transition temperature, which shows a P-type. In the charging stage, the P-type TGC module 2 is subjected to the temperature difference, based on the gelation of cellulose in the electrolyte and the ion induction The complexation effect reaches a high voltage. Secondly, the TREC module 3 is charged at a low voltage at a high temperature. In the cooling stage, the waste heat collection device 1 is disconnected. The overall temperature of the TREC module 3 drops to the initial state of 30°C under the action of the cooling device 4. At this time, the temperature difference between the hot and cold sides of the P / N alternating TGC module 2 is 10K, and the hot side temperature drops below the gelation transition temperature and turns into N type. In the discharge stage, the N-type TGC module 2 is connected to the external circuit, and the battery is discharged to 0V in a short time. The TREC module 3 completes the discharge at a high voltage at a low temperature.

[0057] A heat source and a cold source are respectively provided on the outside of the waste heat collection device 1 and the cooling device 4. The power generated by the TGC module 2 using the temperature difference between the heat source and the TREC module 3 is recorded as W1, the power generated by the TREC module 3 using the temperature difference is recorded as W2, and the power generated by the TGC module 2 using the temperature difference between the cold source and the TREC module 3 is recorded as W3. The heat amount of the heat source is recorded as Q.

[0058] The calculation formula of the average charge and discharge voltage difference obtained by TREC module 3 is:

[0059]

[0060] The formula for calculating the power generation of TREC module 3 in one hour is:

[0061]

[0062] The maximum power generation efficiency calculation formula of TGC module 2 is:

[0063]

[0064] in The thermoelectric figure of merit, that is, the calculation formula for the power generation W1 and W3 corresponding to the thermoelectric coefficient of the material under different working conditions is:

[0065] W1=η max1 Q;

[0066] W3=η max2 Q;

[0067] The calculation formula for the improvement of power generation efficiency of TREC module 3 is:

[0068]

[0069] The temperatures involved in this embodiment are not limited to the above-mentioned cases. In fact, the temperature within the low-grade waste heat range of 0-130 degrees Celsius is applicable and is within the scope of implementation.

[0070] Example 2:

[0071] The overall heat transfer process starts from the heat source, passes through the waste heat collection device 1, N-type TGC module 2, TREC module 3, N-type TGC module 2 and cooling device 4 in sequence, and is finally discharged to the environment.

[0072] First, the waste heat collection device 1 absorbs low-grade waste heat and transfers it to the N-type TGC module 2, and then to the TREC module 3, raising its overall temperature to 60°C. At this point, the temperature difference between the waste heat collection device 1 and the TREC module 3 can be utilized by the TGC module 2. Since the positive electrode material of the TREC module 3 has a negative temperature coefficient and the negative electrode material has a positive temperature coefficient, the open-circuit voltage of the TREC module 3 decreases.

[0073] Then, under the action of the temperature difference, the N-type TGC module 2 reaches a high voltage based on cooperative coordination and hydration. The TREC module 3 is charged at a low voltage at a high temperature and absorbs heat due to entropy increase during the electrochemical reaction. After a period of time, the external load between the waste heat collection device 1 and the N-type TGC module 2 is disconnected. Under the action of the cooling device 4, the overall temperature of the TREC module 3 drops back to the initial state of 30°C, and its open circuit voltage increases. At this time, the temperature difference between the TREC module 3 and the cooling device 4 can be reused by the TGC module 2.

[0074] Finally, the N-type TGC module 2 is reconnected to the external load, and the electrons accumulated on the electrodes flow out. The battery discharges to 0V in a short time. The TREC module 3 completes the discharge at a high voltage at a low temperature. The battery entropy decreases and releases heat to the environment, returning to the original discharge state. Since the charging voltage is lower than the discharging voltage, the charge and discharge energy difference is extracted as the net work W. After completing this cycle, the charge and discharge cycle is repeated multiple times.

[0075] Example 3:

[0076] The overall heat transfer process starts from the heat source, and is transferred in sequence through the waste heat collection device 1, the P / N alternating TGC module 2, the TREC module 3, the P / N alternating TGC module 2 and the cooling device 4, and is finally discharged to the environment.

[0077] First, the waste heat collection device 1 absorbs low-grade waste heat and transfers the heat to the P / N alternating TGC module 2, and then to the TREC module 3, causing its overall temperature to rise to 60°C. At this time, the temperature difference between the waste heat collection device 1 and the TREC module 3 can be utilized by the TGC module 2. At this time, the temperature of the hot side of the TGC module 2 is higher than the gelation transition temperature. The P / N alternating type behaves as a P-type TGC module 2. Since the positive electrode material of the TREC module 3 has a negative temperature coefficient and the negative electrode material has a positive temperature coefficient, the open circuit voltage of the TREC module 3 decreases.

[0078] Then, under the action of the temperature difference, the P-type TGC module 2 reaches a high voltage due to the gelation of cellulose in the electrolyte and the ion-induced complexation. The TREC module 3 is charged at a low voltage at a high temperature and absorbs heat due to entropy increase during the electrochemical reaction. After a period of time, the waste heat collection device 1 is disconnected. The overall temperature of the TREC module 3 drops to the initial state of 30°C under the action of the cooling device 4, and its open circuit voltage increases.

[0079] At this time, the temperature difference between the TREC module 3 and the cooling device 4 can be reused by the TGC module 2. At this time, the hot side temperature of the P-type TGC module 2 is lower than the gelation transition temperature and it is transformed into the N-type TGC module 2. Finally, the N-type TGC module 2 is connected to the external circuit, and the battery is discharged to 0V in a short time. The TREC module 3 completes the discharge at a high voltage at a low temperature. The battery entropy decreases and heat is released to the environment, returning to the original discharge state. Since the charging voltage is lower than the discharging voltage, the charge and discharge energy difference is extracted as the net work W. After completing this cycle, the charge and discharge cycle is repeated multiple times.

[0080] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A thermoelectrochemical waste heat power generation system combined with a thermoelectric cell, comprising a temperature treatment device, a TGC module (2) and a TREC module (3), characterized in that: The temperature treatment device comprises a waste heat collection device (1) and a cooling device (4); a TGC module (2) is installed on one side of the waste heat collection device (1) and the cooling device (4); a TREC module (3) is installed on one side of the TGC module (2); and the waste heat collection device (1), the TGC module (2), the TREC module (3) and the cooling device (4) are electrically connected via a circuit board; The TREC module (3) includes a TREC battery pack and a first heat exchange component, wherein the first heat exchange component is arranged outside the TREC battery pack, the TREC battery pack includes a battery positive electrode, a battery negative electrode, a positive electrode electrolyte, a negative electrode electrolyte and an ion exchange membrane, the ion exchange membrane is arranged between the battery positive electrode and the battery negative electrode, the positive electrode electrolyte is filled between the battery positive electrode and the ion exchange membrane, and the negative electrode electrolyte is filled between the battery negative electrode and the ion exchange membrane; The TGC module (2) comprises a TGC and a second heat exchange component, wherein the second heat exchange component is arranged outside the TGC, the TGC comprises a battery cold electrode, a battery hot electrode and an electrolyte, and the electrolyte is filled between the battery cold electrode and the battery hot electrode; The waste heat collection device (1) includes a heat absorbing medium, which is a common heat-conducting fluid such as water or heat-conducting oil; the cooling device (4) includes a cooling medium, which is water or air; The waste heat collection device (1) and the cooling device (4) further include a heat transfer device, which is a packaged metal heat conducting sheet, heat conducting pipe or heat conducting plate.

2. The thermoelectrochemical waste heat power generation system combined with a thermoelectric cell according to claim 1, characterized in that: The first heat exchange component and the second heat exchange component are both composed of heat exchange plates and heat storage medium, and the heat storage medium is filled into the interior of the heat exchange plates.

3. The thermoelectrochemical waste heat power generation system combined with a thermoelectric cell according to claim 2, characterized in that: The waste heat collection device (1) absorbs three types of low-grade heat, such as industrial waste heat, flue gas waste heat, and data center waste heat, or absorbs solar heat through a heat-absorbing medium in a contact manner. The waste heat collection device (1) sequentially conducts the heat to the inner sides of the second heat exchange component and the first heat exchange component.

4. The thermoelectrochemical waste heat power generation system combined with a thermoelectric cell according to claim 3, characterized in that: After the first heat exchange component absorbs heat, the TREC module (3) can be maintained in a high temperature state, and after the second heat exchange component absorbs heat, the cold and hot electrodes in the TGC module (2) can be maintained in a temperature difference state.

5. The thermoelectrochemical waste heat power generation system combined with a thermoelectric cell according to claim 4, characterized in that: The waste heat collection device (1) and the cooling device (4) are connected in sequence via a TGC module (2) and a TREC module (3); the heat in the waste heat collection device (1) passes through the TGC module (2), the TREC module (3) and the cooling device (4) in sequence; and thermal conductive adhesive is coated between the waste heat collection device (1), the TGC module (2), the TREC module (3) and the cooling device (4).

6. The thermoelectrochemical waste heat power generation system combined with a thermoelectric cell according to claim 5, characterized in that: The models of the TGC module (2) are divided into P type, N type and P / N alternating type.

7. A power generation cycle method for a thermoelectrochemical waste heat power generation system combined with a thermoelectric cell, characterized in that: The following steps are involved: S1: First, the waste heat collection device (1) absorbs low-grade waste heat and transfers the heat to the TGC module (2). The heat source is 70°C, and then transfers the heat to the TREC module (3) to raise its overall temperature to 60°C. At this time, the temperature difference between the waste heat collection device (1) and the TREC module (3) can be used by the TGC module (2). Since the positive electrode material of the TREC module (3) has a negative temperature coefficient and the negative electrode material has a positive temperature coefficient, the open circuit voltage of the TREC module (3) decreases. The TGC module (2) reaches a high voltage under the action of the temperature difference and enters a continuous working mode. The TREC module (3) is charged at a low voltage at a high temperature and absorbs heat due to the increase of entropy during the electrochemical reaction. S2: After a period of time, the waste heat collection device is disconnected, and the cold source is 20°C. At this time, the overall temperature of the TREC module (3) drops to the initial state of 30°C under the action of the cooling device (4), and its open circuit voltage increases. At this time, the temperature difference between the TREC module (3) and the cooling device (4) can be reused by the TGC module (2). Finally, the TGC module (2) is connected to the external circuit, so that the TGC in the TGC module (2) is discharged to 0V in a short time, and the current rises linearly to the maximum value. This is because during the discharge process, electrons flow from the hot side to the cold side through the external circuit, resulting in a decrease in the internal electrostatic field, thereby reducing the battery voltage. The TREC module (3) completes the discharge at a high voltage at a low temperature, and the battery entropy decreases and releases heat to the environment, returning to the original discharge state. Since the charging voltage is lower than the discharging voltage, the charge and discharge energy difference is extracted as the net work W. After completing this cycle, the charge and discharge cycle is repeated many times. S3: Since the TGC module (2) is divided into three types, namely, P type, N type and P / N alternating type, when the TREC module (3) uses the P type TGC module (2) to generate waste heat, in the heating stage, the waste heat is absorbed by the waste heat collection device (1) and then transferred to the P type TGC module (2), and then transferred to the TREC module (3) to raise its overall temperature to 60°C. At this time, the temperature difference between the hot side and the cold side of the P type TGC module (2) is 10K. In the charging stage, the P type TGC module (2) is affected by the temperature difference. Based on the Soret effect and thermoelectric effect to achieve high voltage, the TREC module (3) is charged at low voltage at high temperature. In the cooling stage, the waste heat collection device (1) is disconnected, and the overall temperature of the TREC module (3) is reduced to the initial state of 30°C under the action of the cooling device (4). At this time, the temperature difference between the hot side and the cold side of the P-type TGC module (2) is 10K. In the discharge stage, the P-type TGC module (2) is connected to an external circuit, and the battery is discharged to 0V in a short time. The TREC module (3) completes the discharge at high voltage at low temperature. S4: When the TREC module (3) uses the N-type TGC module (2) to generate waste heat, in the heating stage, the waste heat is absorbed by the waste heat collection device (1) and then transferred to the N-type TGC module (2), and then to the TREC module (3) to raise its overall temperature to 60°C. At this time, the temperature difference between the hot side and the cold side of the N-type TGC module (2) is 10K. At the same time, the hot end of the N-type TGC module (2) is connected to the external load in the circuit, and the current passes through the external load to balance the voltage generated by the ions. In the charging stage, the N-type TGC module (2) is under the action of the temperature difference. Based on The coordinated coordination and hydration achieve high voltage, and then the TREC module (3) is charged at low voltage at high temperature. In the cooling stage, the waste heat collection device (1) and the external load of the N-type TGC module (2) are disconnected. The overall temperature of the TREC module (3) drops to the initial state of 30°C under the action of the cooling device (4). At this time, the temperature difference between the hot side and the cold side of the N-type TGC module (2) is 10K. In the discharge stage, the N-type TGC module (2) is reconnected to the external load, and the battery is discharged to 0V in a short time. The TREC module (3) completes the discharge at high voltage at low temperature. S5: When the TREC module (3) uses the P / N alternating TGC module (2) to generate waste heat, in the heating stage, the waste heat is absorbed by the waste heat collection device (1) and then transferred to the P / N alternating TGC module (2), and then transferred to the TREC module (3) to raise its overall temperature to 60°C. At this time, the temperature difference between the hot side and the cold side of the P / N alternating TGC module (2) is 10K, and the temperature of the hot side is higher than the gelation transition temperature, which shows a P-type. In the charging stage, the P-type TGC module (2) is subjected to the temperature difference, based on the gelation of cellulose in the electrolyte and the ion induction The complexation effect reaches a high voltage, and then the TREC module (3) is charged at a low voltage at a high temperature. In the cooling stage, the waste heat collection device (1) is disconnected, and the overall temperature of the TREC module (3) is reduced to the initial state of 30°C under the action of the cooling device (4). At this time, the temperature difference between the hot side and the cold side of the P / N alternating TGC module (2) is 10K, and the hot side temperature is reduced below the gelation transition temperature and converted to N type. In the discharge stage, the N-type TGC module (2) is connected to an external circuit, and the battery is discharged to 0V in a short time. The TREC module (3) completes the discharge at a high voltage at a low temperature.

8. The power generation cycle method of the thermoelectrochemical waste heat power generation system combined with a thermoelectric cell according to claim 7, characterized in that: The waste heat collection device (1) and the cooling device (4) are provided with a heat source and a cold source on the outside, respectively. The power generation amount of the TGC module (2) using the temperature difference between the heat source and the TREC module (3) is recorded as , the power generation of the TREC module (3) is recorded as The power generation amount of the TGC module (2) using the temperature difference between the cold source and the TREC module (3) is recorded as , the heat of the heat source is recorded as Q; The calculation formula for the average charge and discharge voltage difference obtained by the TREC module (3) is: ； in is the average discharge voltage of the TREC module (3) in S4 at the initial state of 30°C, is the average voltage of the TREC module (3) in S5 when charged at 60°C; The formula for calculating the power generation of the TREC module (3) within one hour is: ； in is the set current for charge and discharge, is the charge and discharge time of the TREC module (3); The maximum power generation efficiency calculation formula of the TGC module (2) is: ； in is the hot side temperature of the TGC module (2), is the cold side temperature of the TGC module (2), is the thermoelectric figure of merit, that is, the power generation corresponding to the thermoelectric coefficient of the material under different working conditions and The calculation formula is: ； ； in is the maximum power generation efficiency of the TGC module (2) when it is in the heating stage, is the maximum power generation efficiency of the TGC module (2) when it is in the cooling stage; The calculation formula for the improvement of the power generation efficiency of the TREC module (3) is: 。

Images