CN112216856A - Hydrochloric acid electrolyte stable at high temperature, preparation method and application thereof - Google Patents
Hydrochloric acid electrolyte stable at high temperature, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a stable hydrochloric acid electrolyte at high temperature, a preparation method and application thereof, wherein the stable hydrochloric acid electrolyte at high temperature comprises an electrolyte main body and a stabilizer, and the concentration of the stabilizer in the stable hydrochloric acid electrolyte at high temperature is less than 0.3 mol/L; the electrolyte main body is pure hydrochloric acid electrolyte or mixed acid electrolyte containing hydrochloric acid, and the stabilizer comprises: organic amine phosphate, sulfuric acid, sulfate, phosphoric acid, phosphate, pyrophosphate and ethanolamine in one or more mixture. The technology can ensure that the HCl-containing all-vanadium electrolyte can stably run for a long time under the conditions of high temperature and high SOC, and solves the problem that the HCl electrolyte is unstable in long-term high-temperature running in the prior art.
Description
Technical Field
The invention relates to the electrolyte technology in the field of energy storage, in particular to a hydrochloric acid electrolyte stable at high temperature, and a preparation method and application thereof.
Background
The large-scale all-vanadium redox flow battery which is widely put into operation at present is mainly pure H2SO4System, but because the vanadium ion is in H2SO4The solubility in the system is limited, and the system is easy to precipitate out, so the concentration of the system is often controlled in<1.7mol/L, resulting in low energy density of the battery system (<18 wh/L). Researchers have developed various types of stabilizers to increase the vanadium concentration in order to improve the high temperature stability of vanadium ions, but the effect is not good. The difficulty lies in that: 1) the stabilizer must be suitable for the solution of two valence states of positive and negative electrodes at the same time, 2) the stabilizer must exist stably and cannot be decomposed by oxidation or reduction.
Vanadium electrolyte of pure HCl system or mixed acid system (prepared by mixing HCl and H) proposed by lililiyu et al in 20132SO4Mixed as supporting electrolyte), can greatly increase the concentration of vanadium ions in the electrolyte solution (>2.4 mol/L), the energy density of the electrolyte can reach 32wh/L, and the stable operation temperature can be increased to 45 ℃, so that the living space of the electrolyte in the energy storage technical field with increasingly severe competition is further expanded, and a plurality of MW-level projects are put into operation at present.
However, it has been found that after a certain period of operation of the HCl-containing electrolyte, if it is desired to further increase the operating temperature to 50 ℃ (further reducing refrigeration costs and increasing energy efficiency), then precipitation of vanadium at 5 valences tends to occur near the cell flow opening; in addition, when the vanadium concentration is increased to >2.50mol/L, when the positive electrode SOC is > 90%, the positive electrode electrolyte is easy to generate crystal precipitation during long-term high-temperature operation. The appearance of precipitation and crystallization presents challenges to further stable applications of HCl-containing, high-concentration vanadium battery systems and high energy density electrolytes.
Disclosure of Invention
The invention aims to provide a hydrochloric acid electrolyte stable at high temperature, aiming at the problem that the existing HCl electrolyte is easy to generate precipitation and crystallization when running at high temperature, so that the electrolyte cannot be stably stored and run.
In order to achieve the purpose, the invention adopts the technical scheme that: a hydrochloric acid electrolyte stable at high temperature comprises an electrolyte main body and a stabilizer, wherein the concentration of the stabilizer in the hydrochloric acid electrolyte stable at high temperature is less than 0.3mol/L, and preferably 0.01-0.2 mol/L;
the electrolyte main body is pure hydrochloric acid electrolyte or mixed acid electrolyte containing hydrochloric acid, and the stabilizer comprises: organic amine phosphates (TETHMP, ATMP), mixtures of one or more of sulfuric acid, sulfates, phosphoric acid, phosphates, pyrophosphates, and ethanolamines.
Further, the electrolyte valence state of the invention is as follows: a valence of 2, 3, 4, 5 or an intermediate valence thereof (e.g., a valence of 3.5). The preferred valence is 3 or 4.
Further, the hydrochloric acid electrolyte stable at high temperature also comprises an activator, and the concentration of the activator is less than 0.3mol/L, and the preferred concentration is less than 0.10 mol/L. The activating agent includes, but is not limited to, one or more of sodium dodecyl benzene sulfonate (SDS), ethylene diamine phosphate and propylene diamine phosphate, and when SDS is used together with the latter two, the co-addition concentration is less than 0.15 mol/L. Further, the stabilizer is one or a mixture of several of phosphoric acid, phosphate and pyrophosphate. 1) Wherein the concentration of the phosphoric acid or the phosphate is less than 0.3mol/L, preferably 0.10-0.15 mol/L. When the two are added together, the total phosphate concentration is less than 0.3mol/L, and preferably 0.05-0.10 mol/L; 2) when the pyrophosphate is added, the total concentration is converted into phosphate radical concentration of less than 0.3mol/L, preferably 0.05-0.10 mol/L; 3) when the phosphoric acid or phosphate and pyrophosphate are mixed and added, the total concentration is less than 0.3mol/L, preferably 0.05-0.10 mol/L.
Further, the electrolyte main body is H of mixed acid electrolyte containing hydrochloric acid2SO4Mixed solution with HCl, H in the mixed acid electrolyte containing hydrochloric acid2SO4The concentration is 0.5-1.5mol/L, and the HCl concentration is 5.0-9.0 mol/L.
The invention also discloses a preparation method of the hydrochloric acid electrolyte stable at high temperature, which comprises the following steps: adding the stabilizer into the electrolyte body according to the concentration (generally, the volume molar concentration, if the stabilizer is a polymer salt, the mole number of the monomer salt can be calculated) at 5-40 ℃, mixing and filtering to prepare the hydrochloric acid electrolyte stable at high temperature.
Furthermore, the effective filtering aperture of a filter bag adopted for filtering is less than 10 μm, so that precipitable substances in the electrolyte can be removed through the filter bag, and the filtering aperture is further controlled to be less than 5 μm.
The invention also discloses application of the hydrochloric acid electrolyte stable at high temperature in an energy storage system of the flow battery.
Further, the hydrochloric acid electrolyte stable at high temperature is applied to the positive electrode and/or the negative electrode of the flow battery energy storage system.
Compared with the prior art, the hydrochloric acid electrolyte stable at high temperature, the preparation method and the application thereof have the following advantages:
1) the hydrochloric acid electrolyte stable at high temperature of the invention is at high temperature>The high-stability high-performance V-shaped alloy has excellent stability when running and stored at 50 ℃ and low temperature (-10 ℃), and can ensure that pure V is obtained5+Stable storage at 50 deg.C, stable operation at 40-50 deg.C for more than 200 cycles, and prolonged stability time of negative electrode at-10 deg.C compared with common control solution>20％。
2) The hydrochloric acid electrolyte stable at high temperature can be applied to the positive electrode or the negative electrode of the energy storage system of the flow battery, and the hydrochloric acid electrolyte stable at high temperature is beneficial to the high-temperature stability of the positive electrode and can also enhance the stability of the negative electrode solution;
3) the stable hydrochloric acid electrolyte at high temperature is used as a positive electrode solution and a negative electrode solution, and can effectively prevent a positive electrode V at high temperature5+Precipitation of ions and negative electrode of vanadium 3V3+The ion is separated out, so that an additive is used for stabilizing the whole system.
4) And (3) performing charge-discharge circulation by adopting Kw-level and 30 kW-level multilayer galvanic piles, and verifying the stability of the electrolyte.
5) And (3) carrying out water bath heat preservation on the electrolyte, and keeping the system solution to operate at a temperature of between 45 and 55 ℃. Every 100 cycles of the interval, sampling and detecting the vanadium concentration mol/L and the efficiency% (CE \ EE \ VE) of the anode and the cathode.
Drawings
FIG. 1 is a process flow for preparing a high temperature resistant HCl-containing electrolyte;
FIG. 2 is a comparison of current efficiencies of an HCl-containing electrolyte containing 0.05mol/L phosphoric acid +0.05mol/L ATMP versus a blank electrolyte;
FIG. 3 is a graph showing the discharge capacity decay rate of an HCl-containing electrolyte containing 0.05mol/L phosphoric acid compared with a blank electrolyte;
FIG. 4 is a comparison of voltage efficiencies of an HCl-containing electrolyte containing 0.07mol/L phosphoric acid +0.1mol/L TETHMP versus a blank electrolyte;
FIG. 5 is a comparison of decay rates of discharge capacities of an HCl-containing electrolyte containing 0.07mol/L phosphoric acid +0.1mol/L TETHMP and a blank electrolyte;
FIG. 6 is a comparison of energy efficiency of HCl-containing electrolyte containing 0.07mol/L phosphoric acid +0.1mol/L TETHMP versus a blank electrolyte.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a hydrochloric acid mixed acid electrolyte stable at high temperature, a formula, a preparation method and an application mode thereof.
In the hydrochloric acid mixed acid electrolyte stable at high temperature of the embodiment, the additive (stabilizer) is a mixture of phosphoric acid and sodium pyrophosphate, the total phosphate radical concentration is 0.08mol/L, and the electrolyte is a mixed acid electrolyte, wherein H is2SO4The concentration is 1.5mol/L, the HCl concentration is 8.5mol/L, and the total vanadium concentration is 2.8 mol/L.
The following experiment is a long-term cycling experiment using a kilowatt-scale battery module, and the performance of a normal electrolyte and the electrolyte after addition of an additive were compared respectively.
FIG. 1 is a flow chart of a preparation process of a high temperature resistant HCl-containing electrolyte.
The following experiment was a pilot test of 30Kw/120kWh (total of plus and minus 7200L electrolyte), and the operating data for the solution after approximately 200 cycles at 50 c is shown in table 1.
Table 1 shows the operating data
The data show that the additive for improving the stability of the positive electrode and the negative electrode of the mixed acid vanadium electrolyte runs for 200 cycles at a high temperature of 50 ℃, other performances of the battery are not influenced, the battery runs normally, the performance is stable, but a system without adding a stabilizer has a weak precipitation phenomenon.
Example 2
The embodiment discloses a pure hydrochloric acid electrolyte stable at high temperature, a formula, a preparation method and an application mode thereof.
In the hydrochloric acid mixed acid electrolyte stable at high temperature, the additive is phosphoric acid with a concentration of 0.05mol/L, and the electrolyte is pure hydrochloric acid electrolyte with a HCl concentration of 9.0mol/L and a total vanadium concentration of 2.6 mol/L. The following experiment is a long-term cycling experiment using a kilowatt-scale battery module, and the performance of a normal electrolyte and the electrolyte after addition of an additive were compared respectively. FIG. 2 is a graph showing the discharge capacity decay rate of an HCl-containing electrolyte containing 0.05mol/L phosphoric acid compared with a blank electrolyte.
The following experiment was a pilot test of 30Kw/120kWh (total 7200L of electrolyte positive and negative), and the solution was subjected to approximately 200 cycles at 50 ℃ for the operating data.
TABLE 2 operating data
The data show that the additive for improving the stability of the positive electrode and the negative electrode of the pure vanadium hydrochloride electrolyte runs for 200 cycles at a high temperature of 50 ℃, other performances of the battery are not influenced, the battery runs normally, the performance is stable, but a system without a stabilizer is precipitated.
Example 3
The embodiment discloses a mixed acid electrolyte stable at high temperature, a formula, a preparation method and an application mode thereof.
This implementationIn the hydrochloric acid mixed acid electrolyte which is stable at high temperature, the additive is organic amine phosphate mixture (TETHMP + ATMP) with the concentration of 0.08mol/L respectively, and the electrolyte is sulfuric acid and hydrochloric acid mixed electrolyte with the HCl concentration of 8.0mol/L and H2SO4The concentration is 1.0 mol/L. The total vanadium concentration was 2.5 mol/L. The following experiments are long-term cycling experiments using kilowatt-scale battery modules, comparing the performance of normal electrolyte and electrolyte with additives.
The following experiment was a pilot test of 30Kw/120kWh (total of plus and minus 7200L electrolyte), and the operating data for the solution after approximately 200 cycles at 50 c is shown in table 3.
TABLE 3 operating data
The data show that the TETHMP and the ATMP are used as additives for improving the stability of the positive electrode and the negative electrode of the pure vanadium hydrochloride electrolyte, 200 cycles are operated at the high temperature of 50 ℃, the system efficiency is normal, and the capacity decay rate is lower than that of a comparison system; the blank system without the addition of stabilizer showed a faint red precipitate.
Example 4
The embodiment discloses a mixed acid electrolyte stable at high temperature, a formula, a preparation method and an application mode thereof.
In the hydrochloric acid mixed acid electrolyte stable at high temperature of the present example, the additive is organic amine phosphate mixture (H)3PO4+ ATMP) with a concentration of 0.05mol/L each, the electrolyte is a mixed electrolyte of sulfuric acid and hydrochloric acid, wherein the HCl concentration is 8.0mol/L, H2SO4The concentration is 0.5 mol/L. The total vanadium concentration was 2.4 mol/L. The following experiment is a long-term cycling experiment using a kilowatt-scale battery module, and the performance of a normal electrolyte and the electrolyte after addition of an additive were compared respectively.
FIG. 2 is a comparison of current efficiencies of an HCl-containing electrolyte containing 0.05mol/L phosphoric acid +0.05mol/L ATMP versus a blank electrolyte.
The following is a pilot test of 2kW/4kWh (240L of electrolyte for both positive and negative electrodes), and the battery charge and discharge operation data after the solution was subjected to about 200 cycles at a temperature of 50 ℃ are shown in Table 4.
TABLE 4 operating data
The data show that phosphoric acid and ATMP are used as additives for improving the stability of the positive electrode and the negative electrode of the pure vanadium hydrochloride electrolyte together, 200 cycles are performed at the high temperature of 50 ℃, the system efficiency is normal, and the capacity decay rate is close; the blank system without the addition of stabilizer showed a faint red precipitate.
Example 5
Dynamic charge and discharge experiment
In the hydrochloric acid mixed acid electrolyte stable at high temperature in this embodiment, the additive is a mixture of sodium pyrophosphate and TETHMP, the TETHMP concentration is 0.1mol/L, and the sodium pyrophosphate concentration is 0.07mol/L in terms of phosphate radical. The following experiments are long-term cycling experiments using kilowatt-scale battery modules, comparing the performance of normal electrolytes and mixed acid electrolytes with additives, respectively.
The following experiment was a pilot test of 30Kw/120kWh (total 7200L of electrolyte positive and negative), and the solution was subjected to approximately 200 cycles at 50 ℃ for the operating data.
TABLE 5 operating data
As seen from the data in Table 5, the additive for improving the stability of the positive electrode and the negative electrode of the mixed acid vanadium electrolyte runs for 200 cycles at a high temperature of 50 ℃, other performances of the battery are not influenced, the battery runs normally, and the performances are stable. However, the control system without the stabilizer has serious red precipitation, which causes the blockage of the anode pipeline and serious attenuation of the discharge capacity at the later stage.
FIG. 1 is a process flow for preparing a high temperature resistant HCl-containing electrolyte;
FIG. 2 is a comparison of current efficiencies of an HCl-containing electrolyte containing 0.05mol/L phosphoric acid +0.05mol/L ATMP and a blank electrolyte, and a curve in the figure shows that the electrolyte containing the proportion has no influence on the current efficiency of the battery;
FIG. 3 is a comparison of discharge capacity decay rates of an HCl electrolyte containing 0.05mol/L phosphoric acid and a blank electrolyte, and it is seen from the graph that the discharge capacity of the HCl electrolyte containing 0.05mol/L phosphoric acid is different from that of the blank electrolyte after 120 cycles, and the discharge capacity decay rate of the solution containing the additive is better than that of the blank electrolyte;
FIG. 4 is a comparison of voltage efficiencies of an HCl-containing electrolyte containing 0.07mol/L phosphoric acid +0.1mol/L TETHMP and a blank electrolyte, and it can be seen from the graph that the voltage efficiency of the electrolyte containing the additive is 2 percent higher than that of the blank solution;
FIG. 5 is a graph showing the comparison of the decay rates of the discharge capacities of the HCl electrolyte containing 0.07mol/L phosphoric acid +0.1mol/L TETHMP and the blank electrolyte, wherein the additive-containing electrolyte maintains the stable discharge capacity at high temperature, and the decay rate is obviously superior to that of the reference electrolyte;
FIG. 6 is a comparison of energy efficiency of HCl-containing electrolyte containing 0.07mol/L phosphoric acid +0.1mol/L TETHMP and blank electrolyte, and it is seen from the figure that the electrolyte with the additive ratio has the same energy efficiency as the reference electrolyte and has no influence on the battery performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The hydrochloric acid electrolyte stable at high temperature is characterized by comprising an electrolyte main body and a stabilizer, wherein the concentration of the stabilizer in the hydrochloric acid electrolyte stable at high temperature is less than 0.3 mol/L;
the electrolyte main body is pure hydrochloric acid electrolyte or mixed acid electrolyte containing hydrochloric acid, and the stabilizer comprises: organic amine phosphate, sulfuric acid, sulfate, phosphoric acid, phosphate, pyrophosphate and ethanolamine in one or more mixture.
2. The high temperature stable hydrochloric acid electrolyte of claim 1, wherein the electrolyte has a valence state of: a valence of 2, 3, 4, 5 or an intermediate valence thereof.
3. The high temperature stable hydrochloric acid electrolyte of claim 1 further comprising an activator, wherein the activator concentration is less than 0.3 mol/L.
4. The high temperature stable hydrochloric acid electrolyte of claim 3 wherein the activator includes but is not limited to sodium dodecyl benzene sulfonate.
5. The hydrochloric acid electrolyte stable at high temperature according to claim 1, wherein the stabilizer is one or a mixture of phosphoric acid and phosphate or pyrophosphate.
6. The hydrochloric acid electrolyte stable at high temperature according to claim 1, wherein the mixed acid electrolyte containing hydrochloric acid as the electrolyte main body is H2SO4Mixed solution with HCl, H in the mixed acid electrolyte containing hydrochloric acid2SO4The concentration is 0.5-1.5mol/L, and the HCl concentration is 5.0-9.0 mol/L.
7. A preparation method of a hydrochloric acid electrolyte stable at high temperature is characterized by comprising the following steps: and adding the stabilizing agent into the electrolyte main body according to the concentration at the temperature of 5-40 ℃, mixing and filtering to prepare the hydrochloric acid electrolyte stable at high temperature.
8. The method of claim 7, wherein the filter bag is used for filtration having an effective filter pore size of <10 μm.
9. Use of the high temperature stable hydrochloric acid electrolyte of any of claims 1 to 6 in a flow battery energy storage system.
10. The use of the high temperature stable hydrochloric acid electrolyte of claim 9 in a flow battery energy storage system, wherein the high temperature stable hydrochloric acid electrolyte is used in a positive electrode and/or a negative electrode of the flow battery energy storage system.
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