CN117747896A - Charging-free thermal regeneration electrochemical cell based on double-membrane structure and use method - Google Patents
Charging-free thermal regeneration electrochemical cell based on double-membrane structure and use method Download PDFInfo
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Abstract
The invention discloses a charging-free thermal regeneration electrochemical cell based on a double-membrane structure and a use method thereof. The electric pair Prussian blue analog with larger temperature coefficient is used as the positive electrode and contains Fe 2+ /Fe 3 The negative electrode forms a primary battery, and the positive electrode potential and the temperature coefficient are regulated and controlled by changing the proportion of metal materials of Prussian blue analogues, the concentration of electrolyte and the intercalation ions, so that the battery can be discharged at high temperature and low temperature through positive-negative electrode conversion, namely the charging-free thermal regeneration electrochemical battery. The temperature coefficient of the battery can reach-2.5 to-3 mV/K, and the voltage, capacity, power density and thermoelectric conversion efficiency of the battery are greatly improved; and effectively block the negative electrode Fe through a double-film structure 2+ /Fe 3+ And ClO 4 ‑ Intercalation and deintercalation of positive ionsIs effective in realizing a stable cycle for a long period of time.
Description
Technical Field
The invention belongs to the field of thermoelectric chemical energy storage and conversion, and particularly relates to a charging-free thermal regeneration electrochemical cell based on a double-membrane structure and a use method thereof.
Background
Low temperature waste heat energy<100 ℃ is widely applied to various industrial production processes and nature. And is increasingly being considered a "renewable energy source" due to its tremendous amount. The low-temperature waste heat energy generated by the main energy consumption departments in China accounts for about 10-20% of the total energy consumption. Therefore, developing a high-efficiency low-temperature waste heat energy utilization technology is beneficial to improving the comprehensive energy efficiency and reducing the carbon emission. The temperature and the temperature difference of the low-temperature waste heat energy are low, and the traditional waste heat recovery technologies such as the organic Rankine cycle and the solid-state thermoelectric generator are difficult to realize efficient utilization. In recent years, liquid thermoelectric cells or systems have attracted considerable attention due to higher efficiency and power density, with the highest thermoelectric conversion efficiency achieved by thermally regenerative electrochemical cycling based on the redox couple seebeck effect. However, conventional thermal regeneration electrochemical cycles require electrical assistance and practical application is limited. The electrochemical cycle of charge-free thermal regeneration adopts an electric pair with similar potential, and can realize high-low temperature simultaneous discharge based on Seebeck effect without charging, but the current research is very little, and an electrochemical system only has PB/Fe (CN) 6 3-/4- And Fe (CN) 6 3-/4- /I - -I 3 - And the battery temperature coefficient is low (alpha cell <1.8 The overall performance is to be improved.
Disclosure of Invention
Aiming at the prior art, the invention provides a charge-free thermal regeneration electrochemical cell based on a double-film structure and a recycling method, namely, adopting an electropair Fe (ClO) with larger positive temperature coefficient (1.5-1.8 mV/K) 4 ) 2 /Fe(ClO 4 ) 3 As a negative electrode, a charging-free thermal regeneration electrochemical cell is constructed by matching electrode potential, prussian blue analogues based on transition metals (one or more of Cu, co, ni and the like) are adopted as a positive electrode, and the positive electrode has a negative temperature coefficient (-0.4 to-1 mV/K), and can realize the regulation and control of the positive electrode potential and the temperature coefficient by changing three schemes of metal material proportion, electrolyte concentration and embedded ions. In addition, due to the negative electrode Fe 2+ /Fe 3+ Can influence the normal embedding and extracting process of the positive Prussian blue analogue material, and ClO 4 - Will be strong in oxidizingLeading to spontaneous extraction of the intercalation ions, the problem is solved by adopting a double-membrane structure, namely, a cation exchange membrane is adopted on the electrolyte side of the positive electrode to prevent ClO 4 - Ion permeation, prevention of Fe by anion exchange membrane on catholyte side 2+ /Fe 3+ Ion permeation, thereby ensuring stable circulation operation under the condition of larger temperature coefficient and voltage of the battery. The invention also develops a series of charging-free thermal regeneration electrochemical cells, and enriches the electrochemical systems in the field.
In order to solve the technical problems, the technical scheme of the invention is that the rechargeable thermal regeneration electrochemical cell based on a double-membrane structure is characterized in that the positive electrode material of the cell is Prussian blue analogues based on transition metal coated on a carbon material, the concentration of positive electrode electrolyte is 0.5-4M, and Na + Embedding or extracting to perform positive electrode oxidation-reduction reaction; the battery cathode material is carbon material, the concentration of the cathode electrolyte is 0.1-1.5M, fe 2+ And Fe (Fe) 3+ Interconversion is carried out to carry out negative electrode oxidation-reduction reaction; an intermediate layer is arranged between the positive electrolyte and the negative electrolyte, the positive electrolyte and the intermediate layer contain the same cations, the negative electrolyte and the intermediate layer contain the same anions and have the same concentration, the intermediate layer is separated from the positive electrolyte by a cation exchange membrane and is used as a cation transmission channel, and the intermediate layer is separated from the negative electrolyte by an anion exchange membrane and is used as an anion transmission channel.
As shown in FIG. 6a, the battery positive electrode material is Prussian blue analogues based on transition metal (one or more of Cu, co and Ni) coated on carbon materials such as carbon felt, carbon cloth or carbon paper, the positive electrode electrolyte is NaCl (concentration is 0.5-4M), na + Embedding or extracting to perform positive electrode oxidation-reduction reaction; the negative electrode material is carbon material such as carbon felt, carbon cloth or carbon paper, and the negative electrode electrolyte is Fe (ClO) 4 ) 2 And Fe (ClO) 4 ) 3 (the concentration is 0.1-1.5M respectively), fe 2+ And Fe (Fe) 3+ Interconversion is carried out to carry out negative electrode oxidation-reduction reaction; an intermediate layer is arranged between the positive electrolyte and the negative electrolyte, and the intermediate layer electrolyte is NaClO 4 (concentration and ClO in negative electrode electrolyte) 4 - Concentration oneResulting) the intermediate layer and the positive electrode electrolyte are separated by a cation exchange membrane as Na + Is separated from the negative electrode electrolyte by an anion exchange membrane as ClO 4 - Is provided for the transmission channel of the optical disk drive.
According to the invention, the Prussian blue analog positive electrode material can be selected from one or more of Cu, co and Ni, and can be selected from Cr, mn, V, fe, zn and In. The anions in the positive electrode electrolyte can be Cl - 、SO 4 2- 、NO 3 - Or ClO 4 - One or more of the following.
The positive ions in the positive electrode electrolyte and the intermediate layer electrolyte can be Na + 、K + 、NH 4 + 、Li + 、Rb + 、Cs + 、Mg 2 + 、Ca 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ One or more of the following.
The anions in the negative electrode and the intermediate layer electrolyte can be ClO 4 - 、SO 4 2- 、NO 3 - Or Cl - One or more of the following. The positive electrode electrolyte, the middle layer and the negative electrode electrolyte can flow.
The second technical scheme of the invention is a method for using a charging-free thermal regeneration electrochemical cell based on a double-membrane structure, which comprises the following steps:
step one: as shown in fig. 6b, the temperature coefficient of the battery is negative, for a specific heat source temperature interval (T 1 -T 2 ) By adjusting the charge state of the Prussian blue analog positive electrode material and the negative electrode Fe 2+ /Fe 3+ At a concentration of (C) such that at an intermediate temperature T 0 ＝(T 1 +T 2 ) At/2, the battery voltage is zero;
step two: as shown in fig. 6b, c and d, process (1) is to change the battery temperature from T 0 Reduced to T 1 Thereby establishing electricityCell voltage alpha cell (T 0 -T 1 ) The positive electrode is Prussian blue analogue, and the negative electrode is Fe 2+ /Fe 3+ ；
Step three: as shown in fig. 6b, c and d, process (2) is that the battery is at low temperature T 1 Discharging under the condition that positive ions are embedded into Prussian blue analogues and negative ions are Fe 2+ Oxidation to Fe 3+ Ending the discharge when the voltage drop is zero;
step four: as shown in fig. 6b, c and d, process (3) is to change the battery temperature from T 1 Raised to T 2 Battery voltage becomes negative-alpha cell (T 2 -T 0 ) By switching between positive and negative electrodes, i.e. the positive electrode is Fe 2+ /Fe 3+ The negative electrode is Prussian blue analogue, and the battery voltage can still be ensured to be positive alpha cell (T 2 -T 0 )；
Step five: as shown in fig. 6b, c and d, process (4) is that the battery is at a high temperature T 2 Discharging under conditions, i.e. Fe 3+ Reduction to Fe 2+ The negative ions are separated from the Prussian blue analogues, and the discharge is ended when the voltage drop is zero;
step six: and (3) repeating the operations from the second step to the fifth step, wherein a charge-free thermal regeneration electrochemical cycle is formed by four processes, and oxidation and reduction reactions are generated in the electrode cycle to continuously store low-temperature thermal energy into chemical energy and convert the chemical energy into electric energy.
According to the method for using the rechargeable thermal regeneration electrochemical cell based on the double-membrane structure, the four processes can be respectively carried out by a plurality of cell modules at the same time. The battery cooling heat in the second step can be used for the battery heating process in the fourth step through one or more heat exchangers.
Compared with other thermal regeneration electrochemical cell technologies, the charging-free thermal regeneration electrochemical cell based on the double-membrane structure and the use method thereof have the beneficial effects that: the invention realizes the regulation and control of the positive electrode potential and the temperature coefficient by changing the proportion of the Prussian blue analog metal material, the concentration of the electrolyte and the embedded ions, thereby leading the battery to discharge at high temperature and low temperature through the conversion between the positive electrode and the negative electrode, i.e. avoiding the charge and the electric heat regenerationA green electrochemical cell. The temperature coefficient of the battery can reach-2.5 to-3 mV/K, and the voltage, capacity, power density and thermoelectric conversion efficiency of the battery are greatly improved; and effectively block the negative electrode Fe through a double-film structure 2+ /Fe 3+ And ClO 4 - The effect on the process of embedding and extracting the positive electrode ions is realized, and long-time stable circulation is realized. A series of charging-free thermal regeneration electrochemical cells with high temperature coefficient are provided by changing the materials of the Prussian blue analogues and the embedded ions, and the continuous and efficient operation of the cells is ensured by the double-membrane structure.
First, by adopting a double-film structure, it is possible to use an electric pair of CuCoNiHCF and Fe (ClO) having a larger temperature coefficient 4 ) 2 /Fe(ClO 4 ) 3 Constructing a charging-free thermal regeneration electrochemical cell, wherein the temperature coefficient theory of the cell reaches-2.5 mV/K, and the temperature coefficient can actually exceed-3 mV/K;
next, fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 Has higher temperature coefficient within the larger concentration range of 0.1-1.5M>1.5mV/K)；
Then, the Prussian blue analog of the positive electrode material can realize the large-scale regulation and control of electrode potential (360-860 mV) and temperature coefficient (-0.4 to-1 mV/K) by changing the proportion of metal materials, the concentration of electrolyte and embedded ions, and a series of charging-free thermal regeneration electrochemical cell systems can be constructed;
preliminary experiments show that when the heat source interval is 20-60 ℃, electricity is used for Cu in one cycle 3 Ni 1 HCF/3M NaCl//6M NaClO 4 //1.2M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 The discharge capacity of the formed charge-free thermal regeneration electrochemical cell can reach 20mAh/g.
Drawings
FIG. 1 (a) Prussian blue analogues CuCoNiHCF and Fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 A temperature coefficient measurement device map; (b) Negative electrode 0.1-1.5M Fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 The potential of the lower electrode of the electrolyte changes with the temperature; (c) The potential of the positive electrode CuNiHCF is changed along with the temperature under the conditions of 50 percent of SOC and 1-4M NaCl electrolyte; (d) The cathode CuCoHCF is electrified under the conditions of 50 percent of SOC and 1M of NaCl electrolyteVariation of the polar potential with temperature; (e) Positive electrode Cu 3 Ni 1 HCF changes with temperature at 50% soc and 1M different intercalation ions.
FIG. 2 (a) charging-free thermally regenerated electrochemical cell Cu 3 Ni 1 HCF/3M NaCl//6M NaClO 4 //1.2M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 A cyclic experiment device diagram; (b) change in battery positive and negative electrode potential with temperature; (c) The battery voltage changes with time in the next cycle at 20-60 ℃; (d) The specific capacity of the battery varies over 50 consecutive cycles at a temperature in the range of 20-60 ℃.
FIG. 3 (a) charging-free thermally regenerated electrochemical cell Cu 1 Co 1 HCF/1M NaCl//6M NaClO 4 //1.2M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 The potential of the positive electrode and the negative electrode changes along with the temperature; (b) Battery voltage changes with time over the next cycle at temperatures ranging from 20-60 c.
FIG. 4 (a) charging-free thermally regenerated electrochemical cell Cu 3 Ni 1 HCF/1M MgCl 2 //5M NaClO 4 //1M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 A cyclic experiment device diagram; (b) change in battery positive and negative electrode potential with temperature; (c) Battery voltage changes with time over the next cycle at temperatures ranging from 20-60 c.
FIG. 5 (a) charging-free thermal regeneration electrochemical flow cell Cu 3 Ni 1 HCF/1M MgCl 2 //5M NaClO 4 //1M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 An exploded view of each part; (b) charge-free thermal regeneration electrochemical flow cell assembly drawing; (c) Battery voltage changes with time over the next cycle at temperatures ranging from 20-60 c.
FIG. 6 (a) Prussian blue analog-based positive electrode and Fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 A schematic of a charge-free thermally regenerated electrochemical cell of a double membrane structure as the negative electrode; (b) The double-film charge-free thermal regeneration electrochemical cell is schematically shown in four working processes (cooling, low-temperature discharging, heating and high-temperature discharging) in one cycle; (c) The double-film charging-free thermal regeneration electrochemical cell is in one cycleSchematic of the change in-loop battery voltage and capacity; (d) The change schematic of the temperature and entropy of the double-film charging-free thermal regeneration electrochemical cell in one cycle
Detailed Description
The present invention will be described in detail below with reference to the drawings and the specific embodiments so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making clear and defining the scope of the present invention.
In the description of the present invention, it should be understood that the terms "one", "a plurality", "a first", "a second", etc. merely denote that the quantity or positional relationship is shown based on the drawings, and are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific quantity and position, operate in a specific quantity and position, and thus should not be construed as limiting the present invention.
Example 1 Prussian blue analogues CuCoNiHCF and Fe (ClO) under different electrode materials, electrolyte concentrations and ion intercalation conditions 4 ) 2 /Fe(ClO 4 ) 3 Measurement of electrode potential and temperature coefficient
First, prussian blue analogues cucopihf and Fe (ClO) under different electrode materials, electrolyte concentrations and ion intercalation conditions 4 ) 2 /Fe(ClO 4 ) 3 Electrode potential and temperature coefficient were measured electronically to obtain optimal selection of temperature coefficient and basis for construction data for a charge-free thermally regenerated electrochemical cell. The temperature coefficient measuring device is shown in fig. 1 (a), namely a constant temperature two-electrode testing system, which comprises a constant temperature circulating water bath, a water bath cup sleeve electrolytic cell (the working electrode is CuCoNiHCF or carbon felt, and the reference electrode is Ag/AgCl) and an electrochemical workstation. As can be seen from FIG. 1 (b), the electric pair Fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 The electrode potential of (2) increases with increasing temperature, i.e. the temperature coefficient is positive and does not vary much with ion concentration, a maximum value of 1.79mV/K is obtained at 1.4M, and the electrode potential is between 530 and 650mV at 40 ℃. The experimental results based on different ratios of CuNiHCF and different concentrations of NaCl are shown in FIG. 1 (c), the higher the Cu ratio in the electrode material, the more the electrode electricityThe higher the potential is, the negative the temperature coefficient of CuNiHCF and the higher the temperature coefficient of electrolyte concentration is, the maximum is about-0.7 mV/K, the electrode potential at 40 ℃ can be regulated between 380 and 700mV, the electrode potential can be overlapped with the Fe side, the construction of a charging-free thermal regeneration electrochemical cell at 20 to 60 ℃ is realized, and other heat source intervals can be met. As shown in FIG. 1 (d), by changing the electrode material to CuCoHCF, the temperature coefficient can be raised to-0.92 mV/K, and the electrode potential range at 40 ℃ is 490-650mV, so that the charging-free thermal regeneration electrochemical cell can be constructed. As shown in fig. 1 (e), based on Cu 3 Ni 1 HCF, other than NaCl, is 1M other ion (e.g., NH 4 Cl、RbCl、MgCl 2 、CaCl 2 、SrCl 2 、BaCl 2 、AlCl 3 ) The optimization and regulation of electrode potential and temperature coefficient can also be realized. In particular RbCl, the temperature coefficient can reach-1 mV/K, but the electrode potential is 870mV (40 ℃) higher, but by reducing the Cu proportion, the electrode potential of NiHCF can be reduced to 640mV (40 ℃), and a charging-free thermal regeneration electrochemical cell with high temperature coefficient (theoretically reaching-2.8 mV/K) can be constructed. In addition, 1M MgCl 2 Lower Cu 3 Ni 1 The temperature coefficient of HCF is also as high as-0.92 mV/K. In summary, the Prussian blue analogues CuCoNiHCF and Fe (ClO 4 ) 2 /Fe(ClO 4 ) 3 A series of charging-free thermal regeneration electrochemical cells which are applicable to different temperature heat source intervals and have large temperature coefficients can be constructed.
Example 2 non-rechargeable thermally regenerated electrochemical cell Cu 3 Ni 1 HCF/3M NaCl//6M NaClO 4 //1.2M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 Cycling process
The capacity of the battery is composed of active material Cu 3 Ni 1 Quality determination of HCF. As shown in FIG. 2 (a), the volume of electrolyte at both sides of the battery experimental device is about 12mL, and Cu is positive electrode 3 Ni 1 HCF is coated on 0.5cm square carbon cloth (the mass of active substance is about 2-3 mg), the negative electrode is 0.5cm square carbon felt (the thickness is 2.5 mm), and the positive electrode and the negative electrode are both fixed by a platinum electrode clamp and connected with an external circuit. The middle layer is made of a silica gel plate with the thickness of 2mm, and positive and negative electrolyte are respectively separated by a positive and negative ion membrane. The battery is a glass water bath cup sleeve and circulates at constant temperatureThe water bath controls the battery temperature. To adapt to the heat source range of 20-60 ℃, cu is respectively selected for the anode and the cathode 3 Ni 1 HCF/3M NaCl and 1.2M Fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 As shown in FIG. 2 (b), the electrode potentials are phase-shifted at 40℃meaning that voltage balance can be achieved at 20℃and 60℃with an interlayer electrolyte of 6M NaClO 4 Ensuring ClO 4 - The concentration is consistent with that of the negative electrode, and the theoretical temperature coefficient of the battery is-2.2 mV/K. One cell cycle involved four processes, as shown in FIG. 2 (c), the cell was first cooled to 20℃, cu 3 Ni 1 HCF is positive electrode, fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 For the negative electrode, a voltage of about 70mV was established, followed by a voltage of 0.1mA (0.4 mA/cm 2 ) Constant current discharge is carried out on the current of the battery, the temperature of the battery is raised to 60 ℃ after the discharge is finished, the voltage is reduced to about-65 mV, at the moment, the anode and the cathode are converted, and Fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 Is positive electrode, cu 3 Ni 1 HCF is used as a negative electrode, and constant current discharge can be carried out. The capacity change for a charge-free thermally regenerated electrochemical cell for 50 consecutive cycles is shown in fig. 2 (d), i.e., the initial capacity of one cycle cell is about 20mAh/g, with decay as the cycle progresses. The experiment shows that the electrochemical cell Cu is regenerated by charging-free heat 3 Ni 1 HCF/3M NaCl//6M NaClO 4 //1.2M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 Charging-free can be realized under low-temperature and high-temperature heat sources, and high voltage is established through a large temperature coefficient, so that electric energy is continuously output outwards.
Example 3 non-rechargeable thermally regenerated electrochemical cell Cu 1 Co 3 HCF/1M NaCl//6M NaClO 4 //1.2M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 Cycling process
In order to examine that a series of non-charging thermal regeneration electrochemical cells can be constructed by electrode materials and electrolyte regulation proposed in the present application, the anode and the electrolyte of the intermediate layer are kept unchanged on the basis of example 2, and the anode materials are introduced into metal Co, namely Cu 1 Co 3 HCF, "1" and "3" indicate a Cu to Co ratio of 1:3, correspondingly reducing the NaCl concentration to1M, as shown in FIG. 3 (a), cu 1 Co 3 HCF/1M NaCl and 1.2M Fe (ClO) 4 ) 2 /Fe(ClO 4 ) 3 The counter electrode potentials intersect at about 30 ℃. According to example 1, increasing the intersection temperature can be achieved by increasing the NaCl concentration. In this example, the battery voltage was zeroed at 40℃to obtain positive electrode Cu 1 Co 3 The SOC of HCF charge state is slightly deviated by 50%, as shown in FIG. 3 (b), at 0.4mA/cm 2 Through four processes of circulation, the charging-free operation can be still realized, and the thermoelectric conversion is realized.
Example 4 non-rechargeable thermally regenerated electrochemical cell Cu 3 Ni 1 HCF/1M MgCl 2 //5M NaClO 4 //1M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 Cycling process
To further increase the temperature coefficient of the charge-free thermally regenerated electrochemical cell, the strategy proposed in this application to modify the intercalation ions was based on example 2 using Mg 2+ Instead of Na + As positive electrode intercalation ions, 1M MgCl is adopted 2 And (3) an electrolyte. As shown in FIG. 4 (a), the battery experimental apparatus diagram is identical to that of example 2, but compared with monovalent ion Na + Divalent ions Mg 2+ Intercalation and deintercalation affect lattice stability, and thus, to increase capacity, the reaction is carried out in 1M MgCl 2 15mM CuCl was added to the electrolyte 2 And 5mM NiCl 2 The solution appeared light blue. To match the positive electrode potential, the negative electrode uses 1M Fe (ClO 4 ) 2 /Fe(ClO 4 ) 3 As shown in FIG. 4 (b), the temperature coefficient theory of the battery can reach-2.5 mV/K, and the intermediate layer electrolyte correspondingly adopts 5M NaClO 4 . As shown in FIG. 4 (b), the concentration of the fluorescent dye was 0.4mA/cm 2 The current density of the battery can realize charge-free and thermoelectric conversion through four circulating processes in a heat source range of 20-60 ℃.
Example 5 charging-free thermal regeneration electrochemical flow cell Cu 3 Ni 1 HCF/1M MgCl 2 //5M NaClO 4 //1M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 Cycling process
Flow batteries are currentlyOne of the most promising energy storage devices mainly benefits from the independent design of achievable power and energy, the power depending on the stack size, and the capacity and energy depending on the volume of electrolyte in the reservoir. According to the method disclosed in claim 6, electrolyte in the rechargeable thermal regeneration electrochemical cell based on the double-membrane structure can flow, and the corresponding flow battery can be constructed. Thus, the charging-free thermally regenerated electrochemical cell Cu proposed based on example 4 3 Ni 1 HCF/1M MgCl 2 //5M NaClO 4 //1M Fe(ClO 4 ) 2 /Fe(ClO 4 ) 3 A corresponding flow battery was constructed as shown in fig. 5 (b). The exploded view of each part of the flow battery is shown in fig. 5 (a), and the flow battery is sequentially provided with an organic glass end plate, a silica gel gasket, a current collector, an electrode and electrode frame, a flow channel, a cation/anion exchange membrane, the silica gel gasket and a tetrafluoro intermediate layer from outside to inside. The current collector is anticorrosive titanium foil and the anode Cu 3 Ni 1 HCF is 1cm square, and the negative electrode is still made of carbon felt. As shown in FIG. 5 (c), the electrolyte circulation was driven by a multichannel peristaltic pump at a flow rate of 1.5mL/min at 0.1mA/cm 2 The current density of the battery can realize charge-free and thermoelectric conversion through four circulating processes in a heat source range of 20-60 ℃.
Table 1 lists electrolyte types of other embodiments than the above-described embodiments, and other working methods are similar to the above-described embodiments.
Table 1 electrolyte combinations for other double membrane structured charge-free thermally regenerative electrochemical cells
Although the invention has been described above with reference to the accompanying drawings, the invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many modifications may be made by those of ordinary skill in the art without departing from the spirit of the invention, which fall within the protection of the invention.
Claims (9)
1. A rechargeable thermal regeneration electrochemical cell based on a double-membrane structure is characterized in that the positive electrode material of the cell is Prussian blue analogues based on transition metal coated on a carbon material, the concentration of positive electrode electrolyte is 0.5-4M, and Na is added into the electrolyte + Embedding or extracting to perform positive electrode oxidation-reduction reaction; the battery cathode material is carbon material, the concentration of the cathode electrolyte is 0.1-1.5M, fe 2+ And Fe (Fe) 3 + Interconversion is carried out to carry out negative electrode oxidation-reduction reaction; an intermediate layer is arranged between the positive electrolyte and the negative electrolyte, the positive electrolyte and the intermediate layer contain the same cations, the negative electrolyte and the intermediate layer contain the same anions and have the same concentration, the intermediate layer is separated from the positive electrolyte by a cation exchange membrane and is used as a cation transmission channel, and the intermediate layer is separated from the negative electrolyte by an anion exchange membrane and is used as an anion transmission channel.
2. The bipolar structured charge-free thermally regenerative electrochemical cell of claim 1 wherein said prussian blue analog positive electrode material is selected from one or more of Cu, co, ni, cr, mn, V, fe, zn and In.
3. The bipolar structured rechargeable thermal regeneration electrochemical cell of claim 1 wherein said positive electrolyte has anions of Cl - 、SO 4 2- 、NO 3 - Or ClO 4 - One or more of the following.
4. A dual membrane structure based charge free thermally regenerative electrochemical cell as claimed in claim 1 whichCharacterized in that the positive electrolyte cation is Na + 、K + 、NH 4 + 、Li + 、Rb + 、Cs + 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2 + 、Al 3+ One or more of the following.
5. The bipolar structured charge-free thermally regenerative electrochemical cell of claim 1 wherein said negative electrolyte anion is ClO 4 - 、SO 4 2- 、NO 3 - Or Cl - One or more of the following.
6. The bipolar structured charge-free thermally regenerative electrochemical cell of claim 1 wherein said positive electrolyte, intermediate layer electrolyte and negative electrolyte are flowable.
7. The method of using a charge-free thermally regenerative electrochemical cell based on a dual membrane structure of claim 1 comprising:
step one: the temperature coefficient of the battery is negative, for a specific heat source temperature interval (T 1 -T 2 ) By adjusting the charge state of the Prussian blue analog positive electrode material and the negative electrode Fe 2+ /Fe 3+ At a concentration of (C) such that at an intermediate temperature T 0 ＝(T 1 +T 2 ) At/2, the battery voltage is zero;
step two: process (1) is to change the battery temperature from T 0 Reduced to T 1 Thereby establishing the battery voltage as alpha cell (T 0 -T 1 )，α cell Is the temperature coefficient of the battery, the positive electrode is Prussian blue analogue, and the negative electrode is Fe 2+ /Fe 3+ ；
Step three: process (2) is that the battery is at low temperature T 1 Discharging under the condition that positive ions are embedded into Prussian blue analogues and negative ions are Fe 2 + Oxidation to Fe 3+ Ending the discharge when the voltage drop is zero;
step four: process (3) is to change the battery temperature from T 1 Raised to T 2 Battery voltage becomes negative-alpha cell (T 2 -T 0 ) By switching between positive and negative electrodes, i.e. the positive electrode is Fe 2+ /Fe 3+ The negative electrode is Prussian blue analogue, and the battery voltage can still be ensured to be positive alpha cell (T 2 -T 0 )；
Step five: process (4) is that the battery is at high temperature T 2 Discharging under conditions, i.e. Fe 3+ Reduction to Fe 2+ The negative ions are separated from the Prussian blue analogues, and the discharge is ended when the voltage drop is zero;
step six: and (3) repeating the operations from the second step to the fifth step, wherein a charge-free thermal regeneration electrochemical cycle is formed by four processes, and oxidation and reduction reactions are generated in the electrode cycle to continuously store low-temperature thermal energy into chemical energy and convert the chemical energy into electric energy.
8. The method of claim 7, wherein the four processes are performed simultaneously by a plurality of battery modules, respectively.
9. The method of claim 7, wherein the battery cooling heat of step two is used in the battery heating process of step four by one or more heat exchangers.
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| CN114400348A (en) * | 2022-01-14 | 2022-04-26 | 天津大学 | Charge-free thermal regeneration electrochemical liquid flow circulating system and working method |
| CN115347252A (en) * | 2022-07-29 | 2022-11-15 | 天津大学 | Environment heat-oxygen capture efficient thermal electrochemical system and working method thereof |
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| CN104364959A (en) * | 2012-06-15 | 2015-02-18 | 特拉华大学 | Multiple-membrane multiple-electrolyte redox flow battery design |
| US20150099150A1 (en) * | 2013-06-18 | 2015-04-09 | Massachusetts Institute Of Technology | Electrochemical systems and methods for harvesting heat energy |
| CN107180946A (en) * | 2017-05-11 | 2017-09-19 | 电子科技大学 | A kind of battery of recyclable low-grade waste heat |
| CN114400348A (en) * | 2022-01-14 | 2022-04-26 | 天津大学 | Charge-free thermal regeneration electrochemical liquid flow circulating system and working method |
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