Electrolyte of a rare earth liquid flow battery and preparation method and application thereof

Abstract

The application provides a kind of electrolyte of rare earth liquid flow battery and its preparation method and application, including: positive electrolyte and negative electrolyte, the active substance of positive electrolyte is selected from first lanthanide series metal element, the active substance of negative electrolyte is selected from second lanthanide series metal element;When the first lanthanide series metal element of positive electrolyte occurs charging electrochemical reaction, the valence of metal element changes from three to four, when discharging electrochemical reaction occurs, the valence of metal element changes from four to three;When the second lanthanide series metal element of negative electrolyte occurs charging electrochemical reaction, the valence of metal element changes from three to two, when discharging electrochemical reaction occurs, the valence of metal element changes from two to three.The application provides a new choice for the comprehensive, recycling and green use of rare earth resources.The prepared battery has simple structure and is easy to scale.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical technology, and in particular to an electrolyte for a rare earth flow battery, a preparation method thereof, and applications thereof. Background Art

[0002] Widespread concern for environmental protection is accelerating the replacement of fossil fuels with renewable energy sources such as solar and wind power. The time-varying nature of solar and wind energy poses challenges to the secure management of power grids. The development of smart grids requires reliable energy storage devices to regulate power input and output for maximum energy efficiency. Among various large-scale energy storage options, pumped hydro and compressed air storage offer the most cost-effective solutions, but they require specialized geographical and geological conditions. Besides these, flow batteries, with their fast response time, rapid charge and discharge capabilities, and high safety, are among the most promising large-scale energy storage devices. In flow batteries, the active material is dissolved in an electrolyte; a pump circulates the electrolyte between the storage tank and the electrode chamber. This structural feature allows for independent power and capacity, significantly increasing system design flexibility and facilitating the fulfillment of diverse customer needs. Currently, flow battery systems under research and development include all-vanadium, sodium polysulfide / bromine, zinc-bromine, and zinc-cerium. All-vanadium liquid flow batteries can avoid the capacity loss problem caused by cross-mixing of positive and negative electrolytes because they use a single element as the energy storage material. The disadvantage is that the standard voltage of a single cell is relatively small (about 1.26V). The energy storage materials used in sodium polysulfide / bromine and zinc-bromine battery systems are cheap and easy to obtain. The disadvantage is that bromine is highly corrosive and can easily cause environmental safety concerns. Zinc-cerium liquid flow batteries have a large single cell voltage (about 2.50V), but the disadvantage is that the effective deposition of negative zinc in a strongly acidic environment faces serious challenges. With the continuous development and utilization of renewable energy, liquid flow batteries will usher in a period of rapid development. Summary of the Invention

[0003] In order to overcome the problems of liquid flow batteries in the prior art and broaden the scope of utilization of rare earth resources, the present invention proposes a positive and negative electrolyte for a rare earth liquid flow battery, and a rare earth liquid flow battery prepared using the electrolyte, which has a long cycle life, is green and environmentally friendly, and has high power density and energy density.

[0004] Specifically, the present invention provides the following technical solutions:

[0005] An electrolyte for a rare earth flow battery, comprising:

[0006] It is composed of a positive electrode electrolyte and a negative electrode electrolyte, wherein the active substance of the positive electrode electrolyte is selected from a first lanthanide metal element, and the active substance of the negative electrode electrolyte is selected from a second lanthanide metal element;

[0007] When the first lanthanide metal element in the positive electrode electrolyte undergoes a charging electrochemical reaction, the valence of the metal element changes from trivalent to tetravalent, and when the discharge electrochemical reaction occurs, the valence of the metal element changes from tetravalent to trivalent;

[0008] When the second lanthanide metal element in the negative electrode electrolyte undergoes a charging electrochemical reaction, the valence of the metal element changes from trivalent to divalent, and when the discharge electrochemical reaction occurs, the valence of the metal element changes from divalent to trivalent.

[0009] Furthermore, the first lanthanide metal element is selected from at least one of Ce, Pr, Tb, and Dy; and the second lanthanide metal element is selected from at least one of Sm, Eu, Tm, and Yb.

[0010] Furthermore, the positive electrode electrolyte includes a first lanthanide metal element, a first acid, and 0-0.5 wt% polyacrylamide and / or 0-0.5 wt% polyacrylic acid. Polyacrylamide and polyacrylic acid are stabilizers for the electrolyte, and one or both of them can be added to the positive electrode electrolyte. The hydrogen ion concentration in the positive electrode electrolyte is 0.02-10 M. The concentration of each first lanthanide metal element in the positive electrode electrolyte is 0.02-6.0 M.

[0011] The negative electrode electrolyte includes a second lanthanide metal element, a second type of acid, 0-0.25M zinc ions, 0-2.0M NaHSO3, 0-2.0M NaHSO4, and 0-2.0M Na2S2O4; all four substances have the function of increasing the conductivity of the solution. In addition, zinc ions can inhibit the hydrogen evolution reaction at the negative electrode. NaHSO3 and Na2S2O4 have the function of removing dissolved oxygen from the electrolyte. Their added concentrations must take into account the dissolved oxygen concentration in the electrolyte and the concentration of the electrode reaction active substances, and are not conventional choices; the hydrogen ion concentration in the negative electrode electrolyte is 0.02-10M.

[0012] Furthermore, the positive electrode electrolyte further comprises an active substance for the negative electrode electrolyte, wherein the second lanthanide metal element in the positive electrode electrolyte is in a +3 valence state; and / or the negative electrode electrolyte further comprises an active substance for the positive electrode electrolyte, wherein the first lanthanide metal element in the negative electrode electrolyte is in a +3 valence state. By including the negative electrode electrolyte active substance in the positive electrode electrolyte or the positive electrode electrolyte active substance in the negative electrode electrolyte, the battery capacity can be maintained constant. The negative electrode active substance in the positive electrode electrolyte does not participate in the electrode reaction, and the positive electrode active substance in the negative electrode electrolyte does not participate in the electrode reaction either. They only play a role in material balance, which helps to maintain the battery capacity.

[0013] The present invention also provides a method for preparing a positive electrode electrolyte, comprising:

[0014] Step S1, weigh the salt of the first lanthanide metal and the optional oxide of the second lanthanide metal, and add a certain amount of water;

[0015] Step S2, add the first type of acid to the solution obtained in step S1 and stir thoroughly; those skilled in the art can understand that at this time, the salt of the first lanthanide metal and the optional oxide of the second lanthanide metal will be fully dissolved by the acid;

[0016] Optionally, polyacrylamide and / or polyacrylic acid are further added after the addition of the first type of acid; those skilled in the art can understand that polyacrylamide and / or polyacrylic acid are selected according to actual needs.

[0017] Step S3, add the balance of water to the solution obtained in step S2 to make up the volume.

[0018] Those skilled in the art can understand that in steps S1-S3, there is a stirring step when adding the raw material substances for preparing the electrolyte in each step, so that the raw materials are more uniformly mixed.

[0019] Meanwhile, the present application can also select the following way when preparing the positive electrolyte:

[0020] Step S1, weigh the salt of the first lanthanide metal and the optional oxide of the second lanthanide metal, and add a certain amount of water;

[0021] Step S2, add a certain amount of the first type of acid again; optionally, polyacrylamide and / or polyacrylic acid are further added thereafter;

[0022] Step S3, add water to make up the volume.

[0023] Further, the salt of the first lanthanide metal is preferably a carbonate; the first type of acid is selected from at least one of nitric acid, methyl sulfonic acid, trifluoromethyl sulfonic acid, and trifluoroacetic acid.

[0024] The present application also provides a preparation method of a negative electrolyte, comprising:

[0025] Step S1', weigh the oxide of the second lanthanide metal and the optional salt of the first lanthanide metal, and add a certain amount of water;

[0026] Step S2', add the second type of acid to the solution obtained in step S1 and stir thoroughly; those skilled in the art can understand that at this time, the oxide of the second lanthanide metal and the optional salt of the first lanthanide metal will be fully dissolved by the acid;

[0027] Optionally, zinc salt, NaHSO 3 , NaHSO 4 and Na 2 S 2 O 4 are further added after adding the second type of acid; those skilled in the art will appreciate that the addition of zinc salt, NaHSO 3 , NaHSO 4 and Na 2 S 2 O 4 is optional based on actual needs.

[0028] Step S3', adding the remaining amount of water to the solution obtained in step S2' to make up the volume.

[0029] Those skilled in the art will appreciate that, in steps S1 to S3', a stirring step may be performed at each step when adding raw materials for preparing the electrolyte to ensure more uniform mixing of the raw materials.

[0030] At the same time, the present invention can also select the following method when preparing the negative electrode electrolyte:

[0031] Step S1′, weighing the oxide of the second lanthanide metal and the optional salt of the first lanthanide metal, dissolving them in the second type of acid in a stoichiometric ratio, and stirring thoroughly;

[0032] Step S2', adding a certain amount of the second type of acid again;

[0033] Optionally, add zinc salt and mix well, then add NaHSO3, NaHSO4, and Na2S2O4 and mix well;

[0034] Step S3', add water to make up the volume.

[0035] Furthermore, the salt of the first lanthanide metal is preferably a carbonate; the second acid is selected from at least one of hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, or trifluoroacetic acid. This is because the electrode potential borne by the negative electrode electrolyte is different from that of the positive electrode electrolyte. Some acids, such as hydrochloric acid, are stable at the negative electrode but unstable at the positive electrode; the zinc salt is preferably zinc chloride.

[0036] The present invention also provides a rare earth liquid flow battery, comprising: a negative electrode, a negative electrode electrolyte, a positive electrode, a positive electrode electrolyte and an ion exchange membrane (ie, a diaphragm).

[0037] The positive and negative electrodes of the battery can be made of inert materials such as carbon felt, graphite felt, graphite plate, graphite paper, or carbon cloth. An ion exchange membrane separates the battery cells into positive and negative compartments, with the positive electrode in the positive compartment and the negative electrode in the negative compartment. The ion exchange membrane is a cation exchange membrane.

[0038] Preferably, a plurality of rare earth flow battery cells are connected to form a battery stack.

[0039] Optionally, the positive electrode electrolyte is placed in the positive electrode tank, and the positive electrode chamber is connected to the positive electrode tank and the first pump through a first electrolyte conduit to form a loop, and the positive electrode electrolyte circulates in the loop.

[0040] The negative electrode electrolyte is placed in the negative electrode tank, and the negative electrode chamber is connected to the negative electrode tank and the second pump through a second electrolyte conduit to form a loop, and the negative electrode electrolyte circulates in the loop.

[0041] During the charge and discharge process of the rare earth flow battery of this invention, positive and negative electrolytes are continuously pumped into the battery cells by positive and negative electrolyte delivery pumps, respectively. The flow of electrolyte accelerates the mass transfer process at the electrode interface, which helps reduce electrochemical and concentration polarization in the electrode reaction. The rated power of the battery depends on the size of the stack, while the capacity is determined by the volume and concentration of the electrolyte.

[0042] When the rare earth liquid flow battery of the present invention is charged and discharged, the negative and positive electrolytes in the negative and positive electrode tanks are driven by the electrolyte delivery pumps, enter the negative and positive electrode chambers through the electrolyte conduits to carry out electrode reactions, and then flow back to the negative and positive electrode tanks.

[0043] The rare earth liquid flow battery of the present invention has the following electrode reactions and battery reactions:

[0044] Negative electrode reaction:

[0045]

[0046] or (and)

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[0048] or (and)

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[0050] or (and)

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[0052] Positive electrode reaction:

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[0054] or (and)

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[0058] or (and)

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[0060] Battery reaction:

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[0092] The beneficial effects brought about by the technical solution provided by the present invention include at least:

[0093] The rare earth flow battery of this invention innovates the design of its active components, improves the formulation of its electrolyte, and provides multiple new options for constructing rare earth flow batteries. This invention offers new options for the comprehensive, circular, and green utilization of rare earth resources. Rare earth flow batteries boast a simple structure, easy scalability, long cycle life, high power density, energy density, and energy utilization efficiency. They can be used as large-scale electrical energy storage and efficient conversion devices in wind and solar power generation systems, and have broad application prospects in industries such as electricity and transportation. BRIEF DESCRIPTION OF THE DRAWINGS

[0094] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0095] Figure 1 This is a schematic structural diagram of a rare earth flow battery cell of the present invention;

[0096] Wherein: 1-negative electrode, 2-positive electrode, 3-negative electrode tank, 4-positive electrode tank, 5-negative electrode liquid pump, 6-positive electrode liquid pump, 7-ion exchange membrane, 8-negative electrode electrolyte conduit, 9-external power supply or load, 10-negative electrode chamber, 11-positive electrode chamber, 12-positive electrode electrolyte conduit. DETAILED DESCRIPTION

[0097] In order to make the purpose, technical solutions and advantages of the present invention more clear, the technical solutions of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0098] like Figure 1 As shown (the arrows in the figure indicate the direction of electrolyte flow), the rare earth liquid flow battery of the present invention is mainly composed of a stack of multiple battery cells consisting of a negative electrode 1, a negative electrode electrolyte, a positive electrode 2, a positive electrode electrolyte and an ion exchange membrane (diaphragm) 7. The negative electrode electrolyte is placed in a negative electrode tank 3 and is transported by a negative electrode liquid pump 5. The positive electrode electrolyte is placed in a positive electrode tank 4 and is transported by a positive electrode liquid pump 6. The negative electrode chamber 10 in the stack is connected to the negative electrode tank and the negative electrode electrolyte delivery pump by a negative electrode electrolyte conduit 8 to form a loop, and the negative electrode electrolyte circulates in the loop. The positive electrode chamber 11 in the stack is connected to the positive electrode tank and the positive electrode electrolyte delivery pump by a positive electrode electrolyte conduit 12 to form a loop, and the positive electrode electrolyte circulates in the loop. The load or external power supply 9 is connected to the negative electrode 1 and the positive electrode 2.

[0099] The negative electrode electrolyte is 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0MTm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Ce 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Pr 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0MNa2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Tb 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3 + / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Dy 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0MSm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Ce 3+ and 0.02-6.0M Pr 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+and 0.02-6.0M Ce 3+ and 0.02-6.0M Tb 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 2+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Ce 3+ and 0.02-6.0M Dy 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3 + / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Pr 3+ and 0.02-6.0M Tb 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0MNa2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Pr 3+and 0.02-6.0M Dy 3+ and 0.02-10M H + and 0-0.25MZn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0MTb 3+ and 0.02-6.0M Dy 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 2+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0MTm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Ce 3+ and 0.02-6.0M Pr 3+ and 0.02-6.0M Tb 3+ and 0.02-10M H + and 0-0.25M Zn 2+ and 0-2.0M NaHSO3 and 0-2.0M NaHSO4 and 0-2.0M Na2S2O4, or 0.02-6.0M Sm 3+ / Sm 2+ or (and) 0.02-6.0M Eu 3+ / Eu 2+ or (and) 0.02-6.0M Tm 3+ / Tm 2+ or (and) 0.02-6.0M Yb 3+ / Yb 2+ and 0.02-6.0M Ce 3+and 0.02-6.0 M Pr 3+ and 0.02-6.0 M Dy 3+ and 0.02-10 M H + and 0-0.25 M Zn 2+ and 0-2.0 M NaHSO3 and 0-2.0 M NaHSO4 and 0-2.0 M Na2S2O4, or 0.02-6.0 M Sm 3+ / Sm 2+ or (and) 0.02-6.0 M Eu 3+ / Eu 2+ or (and) 0.02-6.0 M Tm 3+ / Tm 2+ or (and) 0.02-6.0 M Yb 3+ / Yb 2+ and 0.02-6.0 M Pr 3+ and 0.02-6.0 M Tb 3+ and 0.02-6.0 M Dy 3+ and 0.02-10 M H + and 0-0.25 M Zn 2+ and 0-2.0 M NaHSO3 and 0-2.0 M NaHSO4 and 0-2.0 M Na2S2O4, or 0.02-6.0 M Sm 3+ / Sm 2+ or (and) 0.02-6.0 M Eu 3+ / Eu 2+ or (and) 0.02-6.0 M Tm 3+ / Tm 2+ or (and) 0.02-6.0 M Yb 3+ / Yb 2+ and 0.02-6.0 M Ce 3+ and 0.02-6.0 M Pr 3+ and 0.02-6.0 M Tb 3+ and 0.02-6.0 M Dy 3+ and 0.02-10 M H + and 0-0.25 M Zn 2+ and 0-2.0 M NaHSO3 and 0-2.0 M NaHSO4 and 0-2.0 M Na2S2O4, or 0.02-6.0 M Sm

[0100] positive electrolyte is 0.02-6.0 M Ce 4+ / Ce 3+ or (and) 0.02-6.0 M Pr 4+ / Pr 3+or (and) 0.02-6.0MTb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Sm 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0MTb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Eu 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Tm 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4 + / Pr 3+or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Yb 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0MSm 3+ and 0.02-6.0M Eu 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Sm 3+ and 0.02-6.0M Tm 3+ and 0.02-10M H+ and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Sm 3+ and 0.02-6.0M Yb 3+ and 0.02-10MH +and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Eu 3+ and 0.02-6.0M Tm 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0MDy 4+ / Dy 3+ and 0.02-6.0M Eu 3+ and 0.02-6.0M Yb 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0MTb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Tm 3+ and 0.02-6.0M Yb 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0MPr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Sm 3+ and 0.02-6.0M Eu 3+ and 0.02-6.0M Tm 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Sm 3+ and 0.02-6.0M Eu 3+ and 0.02-6.0M Yb 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0MPr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Eu 3+ and 0.02-6.0M Tm 3+ and 0.02-6.0M Yb 3+ and 0.02-10M H + and 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid, or 0.02-6.0M Ce 4+ / Ce 3+ or (and) 0.02-6.0M Pr 4+ / Pr 3+ or (and) 0.02-6.0M Tb 4+ / Tb 3+ or (and) 0.02-6.0M Dy 4+ / Dy 3+ and 0.02-6.0M Sm 3+ and 0.02-6.0M Eu3+ and 0.02-6.0M Tm 3+ and 0.02-6.0MYb 3+ and 0.02-10M H + and an aqueous solution of 0-0.5% polyacrylamide and / or 0-0.5% polyacrylic acid.

[0101] The negative electrode electrolyte is selected from Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Ce2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Pr2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Tb2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Dy2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Ce2(CO3)3 and Pr2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Ce2(CO3)3 and Tb2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Ce2(CO3)3 and Dy2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and P r2(CO3)3 and Tb2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Pr2(CO3)3 and Dy2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Tb2(CO3)3 and Dy2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Ce2(CO3)3 and Pr2(CO3)3 and Tb2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2 O3 or (and) Yb2O3 and Ce2(CO3)3 and Pr2(CO3)3 and Dy2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Pr2(CO3)3 and Tb2(CO3)3 and Dy2(CO3)3, or Sm2O3 or (and) Eu2O3 or (and) Tm2O3 or (and) Yb2O3 and Ce2(CO3)3 and Pr2(CO3)3 and Tb2(CO3)3 and Dy2(CO3)3 are selected, dissolved in acid, and the required amount of zinc salt, sodium bisulfite, sodium bisulfate and sodium dithionite are added to obtain.

[0102] Positive electrode electrolyte, select Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3, or select Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Sm2O3, or select Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Eu2O3, or select Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Tm2O3, or select Ce2(CO3)3 or (and )Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Yb2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Sm2O3 and Eu2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Sm2O3 and Tm2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Sm2O3 and Yb2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Eu2O3 and Tm2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Eu2O3 and Yb2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Tm2O3 and Yb2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Sm2O3 and Eu2O3 and Tm2 O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Sm2O3 and Eu2O3 and Yb2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Eu2O3 and Tm2O3 and Yb2O3, or Ce2(CO3)3 or (and) Pr2(CO3)3 or (and) Tb2(CO3)3 or (and) Dy2(CO3)3 and Sm2O3 and Eu2O3 and Tm2O3 and Yb2O3, dissolved in acid, and the required amount of polyacrylamide and / or polyacrylic acid is added to obtain.

[0103] The positive and negative electrodes of the battery cells can be made of inert materials such as carbon felt, graphite felt, graphite sheet, graphite paper, or carbon cloth. An ion exchange membrane separates the battery cells into a positive and negative electrode compartments, with the positive electrode in the positive compartment and the negative electrode in the negative compartment. The ion exchange membrane is a cation exchange membrane.

[0104] During the charge and discharge process of the rare earth flow battery of this invention, positive and negative electrolytes are continuously pumped into the battery cells by positive and negative electrolyte delivery pumps, respectively. The flow of electrolyte accelerates the mass transfer process at the electrode interface, which helps reduce electrochemical and concentration polarization in the electrode reaction. The rated power of the battery depends on the size of the stack, while the capacity is determined by the volume and concentration of the electrolyte.

[0105] When the rare earth liquid flow battery of the present invention is charged and discharged, the negative and positive electrolytes in the negative and positive electrode tanks are driven by the electrolyte delivery pumps, enter the negative and positive electrode chambers through the electrolyte conduits to carry out electrode reactions, and then flow back to the negative and positive electrode tanks.

[0106] Example 1: Prepare 100mL of 6.0M SmCl3, 1.0M HCl, 1.0M H2SO4, 1.0M CH3SO3H, 1.0MCF3SO3H, 1.0M HAc, 1.0M CF3COOH, 0.1M ZnCl2, 0.1M NaHSO3, 0.1M NaHSO4, and 0.1MNa2S2O4 negative electrolyte.

[0107] First, weigh 0.3 mol Sm2O3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 1.9 mol HCl, 0.1 mol H2SO4, 0.1 mol CH3SO3H, 0.1 mol CF3SO3H, 0.1 mol HAc, and 0.1 mol CF3COOH, and stir thoroughly; then add 0.01 mol ZnCl2, 0.01 mol NaHSO3, 0.01 mol NaHSO4, and 0.01 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0108] Example 2: Prepare 100mL of 6.0M Eu(CH3SO3)3 and 1.0M HCl and 1.0M H2SO4 and 1.0M CH3SO3H and 1.0M CF3SO3H and 1.0M HAc and 1.0M CF3COOH and 0.1M ZnCl2 and 0.1M NaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 negative electrolyte.

[0109] First, weigh 0.3 mol Eu2O3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HCl, 0.1 mol H2SO4, 1.9 mol CH3SO3H, 0.1 mol CF3SO3H, 0.1 mol HAc, and 0.1 mol CF3COOH, and stir thoroughly; then add 0.01 mol ZnCl2, 0.01 mol NaHSO3, 0.01 mol NaHSO4, and 0.01 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0110] Example 3: Prepare 100 mL of 6.0 M TmAc3, 1.0 M HCl, 1.0 M H2SO4, 1.0 M CH3SO3H, 1.0 M CF3SO3H, 1.0 M HAc, 1.0 M CF3COOH, 0.1 M ZnCl2, 0.1 M NaHSO3, 0.1 M NaHSO4, and 0.1 M Na2S2O4 negative electrolyte.

[0111] First, weigh 0.3 mol Tm2O3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HCl, 0.1 mol H2SO4, 0.1 mol CH3SO3H, 0.1 mol CF3SO3H, 1.9 mol HAc, and 0.1 mol CF3COOH, and stir thoroughly; then add 0.01 mol ZnCl2, 0.01 mol NaHSO3, 0.01 mol NaHSO4, and 0.01 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0112] Example 4: Prepare 100mL of 6.0M Yb(CF3COO)3 and 1.0M HCl and 1.0M H2SO4 and 1.0M CH3SO3H and 1.0M CF3SO3H and 1.0M HAc and 1.0M CF3COOH and 0.1M ZnCl2 and 0.1M NaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 negative electrolyte.

[0113] First, weigh 0.3 mol Yb2O3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HCl, 0.1 mol H2SO4, 0.1 mol CH3SO3H, 0.1 mol CF3SO3H, 0.1 mol HAc, and 1.9 mol CF3COOH, and stir thoroughly; then add 0.01 mol ZnCl2, 0.01 mol NaHSO3, 0.01 mol NaHSO4, and 0.01 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0114] Example 5: Prepare 100mL of 3.0M SmCl3 and 3.0M Ce(CH3SO3)3 and 2.0M H2SO4 and 6.0M CF3SO3H and 0.25M ZnCl2 and 0.2M NaHSO3 and 0.2M NaHSO4 and 0.2M Na2S2O4 negative electrode electrolyte.

[0115] First, weigh 0.15 mol Sm2O3 and 0.15 mol Ce2(CO3)3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.9 mol HCl, 0.2 mol H2SO4, 0.9 mol CH3SO3H, and 0.6 mol CF3SO3H, and stir thoroughly; then add 0.025 mol ZnCl2, 0.02 mol NaHSO3, 0.02 mol NaHSO4, and 0.02 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0116] Example 6: Prepare 100 mL of 3.0 M EuAc 3 , 3.0 M Pr(CF 3 SO 3 ) 3 , 5.0 M HCl , 5.0 M CH 3 SO 3 H , 0.25 M ZnCl 2 , 0.2 M NaHSO 3 , 0.2 M NaHSO 4 , and 0.2 M Na 2 S 2 O 4 negative electrode electrolyte.

[0117] First, weigh 0.15 mol Eu2O3 and 0.15 mol Pr2(CO3)3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.5 mol HCl, 0.5 mol CH3SO3H, 0.9 mol CF3SO3H, and 0.9 mol HAc, and stir thoroughly; then add 0.025 mol ZnCl2, 0.02 mol NaHSO3, 0.02 mol NaHSO4, and 0.02 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0118] Example 7: Prepare 100 mL of 3.0 M TmAc 3 , 3.0 M Tb(CF 3 SO 3 ) 3 , 2.0 M HCl , 0.25 M ZnCl 2 , 0.2 M NaHSO 3 , 0.2 M NaHSO 4 , and 0.2 M Na 2 S 2 O 4 negative electrode electrolyte.

[0119] First, weigh 0.15 mol Tm2O3 and 0.15 mol Tb2(CO3)3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.2 mol HCl, 0.9 mol CF3SO3H, and 0.9 mol HAc, and stir thoroughly; then add 0.025 mol ZnCl2, 0.02 mol NaHSO3, 0.02 mol NaHSO4, and 0.02 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0120] Example 8: Prepare 100 mL of 3.0 M YbAc 3 , 3.0 M Dy(CF 3 COO) 3 , 2.0 M H 2 SO 4 , 0.25 M ZnCl 2 , 0.2 M NaHSO 3 , 0.2 M NaHSO 4 , and 0.2 M Na 2 S 2 O 4 negative electrode electrolyte.

[0121] First, weigh 0.15 mol Yb2O3 and 0.15 mol Dy2(CO3)3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.9 mol HAc, 0.9 mol CF3COOH, and 0.2 mol H2SO4, and stir thoroughly; then add 0.025 mol ZnC12, 0.02 mol NaHSO3, 0.02 mol NaHSO4, and 0.02 mol Na2S2O4, add water to make the solution 100 mL, and stir thoroughly to obtain the required electrolyte.

[0122] Example 9: Prepare 100mL of 3.0M SmCl3 and 1.5M Eu2(SO4)3 and 3.0M CeAc3 and 3.0M Pr(CF3COO)3 and 5.0M CH3SO3H and 0.25M ZnCl2 and 0.2M NaHSO3 and 0.2M NaHSO4 and 0.2M Na2S2O4 negative electrode electrolyte.

[0123] First, weigh 0.15 mol Sm2O3, 0.15 mol Eu2O3, 0.15 mol Ce2(CO3)3 and 0.15 mol Pr2(CO3)3, put them in a 250 mL beaker, add 30 mL of water and stir thoroughly; then add 0.9 mol HCl, 0.45 mol H2SO4, 0.9 mol HAc, 0.9 mol CF3COOH and 0.5 mol CH3SO3H and stir thoroughly; then add 0.025 mol ZnCl2, 0.02 mol NaHSO3, 0.02 mol NaHSO4 and 0.02 mol Na2S2O4, add water to make the solution 100 mL, stir thoroughly to obtain the required electrolyte.

[0124] Example 10: Prepare 100mL of 3.0M TmCl3, 1.5MYb2(SO4)3, 3.0M TbAc3, 3.0M Dy(CF3COO)3, 5.0M CF3SO3H, 0.25M ZnCl2, 0.2M NaHSO3, 0.2M NaHSO4 and 0.2M Na2S2O4 negative electrode electrolyte.

[0125] First, weigh 0.15 mol Tm2O3, 0.15 mol Yb2O3, 0.15 mol Tb2(CO3)3 and 0.15 mol Dy2(CO3)3, put them in a 250 mL beaker, add 30 mL water and stir thoroughly; then add 0.9 mol HCl, 0.45 mol H2SO4, 0.9 mol HAc, 0.9 mol CF3COOH and 0.5 mol CF3SO3H and stir thoroughly; then add 0.025 mol ZnCl2, 0.02 mol NaHSO3, 0.02 mol NaHSO4 and 0.02 mol Na2S2O4, add water to make the solution 100 mL, stir thoroughly to obtain the required electrolyte.

[0126] Example 11: Prepare 100mL of 3.0M SmCl3, 0.01M Eu2(SO4)3, 0.02M Tm(CH3SO3)3, 3.0MCeAc3, 0.02M Pr(CF3COO)3, 0.02M TbCl3, 5.0M CH3SO3H, 5.0MCF3COOH, 0.1M ZnCl2, and 0.1M Na2S2O4 negative electrolyte.

[0127] First, take 0.15 mol Sm2O3and 0.001 mol Eu2O3and 0.001 mol Tm2O3and 0.15 mol Ce2(CO3)3and 0.001 mol Pr2(CO3)3and 0.001 mol Tb2(CO3)3, put them in a 250 mL beaker, add 30 mL water, stir well; then add 0.906 mol HCl and 0.003 mol H2SO4and 0.506 mol CH3SO3H and 0.9 mol HAc and 0.506 mol CF3COOH, stir well; add 0.01 mol ZnCl2and 0.01 mol Na2S2O4, add water to 100 mL, stir well, and the desired electrolyte is obtained.

[0128] Example 12: Prepare 100 mL of 3.0 M SmCl3and 0.01 M Eu2(SO4)3and 0.02 M Yb(CF3SO3)3and 3.0 M CeAc3and 0.02 M Pr(CF3COO)3and 0.01 M Dy2(SO4)3and 5.0 M CH3SO3H and 5.0 M CF3COOH and 0.1 M ZnCl2and 0.1 M NaHSO3and 0.1 M NaHSO4negative electrolyte.

[0129] First, take 0.15 mol Sm2O3and 0.001 mol Eu2O3and 0.001 mol Yb2O3and 0.15 mol Ce2(CO3)3and 0.001 mol Pr2(CO3)3and 0.001 mol Dy2(CO3)3, put them in a 250 mL beaker, add 30 mL water, stir well; then add 0.9 mol HCl and 0.06 mol H2SO4and 0.5 mol CH3SO3H and 0.06 mol CF3SO3H and 0.9 mol HAc and 0.506 mol CF3COOH, stir well; add 0.01 mol ZnCl2and 0.01 mol NaHSO3and 0.01 mol NaHSO4, add water to 100 mL, stir well, and the desired electrolyte is obtained.

[0130] Example 13: Prepare 100 mL of 0.02 M SmCl3and 0.02 M Tm(CH3SO3)3and 3.0 M Yb(CF3SO3)3and 0.02 M CeAc3and 0.02 M TbCl3and 1.5 M Dy2(SO4)3and 5.0 M CH3SO3H and 5.0 M CF3COOH and 0.1 M NaHSO3and 0.1 M NaHSO4and 0.1 M Na2S2O4negative electrolyte.

[0131] First, take 0.001 mol of Sm2O3 and 0.001 mol of Tm2O3 and 0.15 mol of Yb2O3 and 0.001 mol of Ce2(CO3)3 and 0.001 mol of Tb2(CO3)3 and 0.15 mol of Dy2(CO3)3, put them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.012 mol of HCl and 0.506 mol of CH3SO3H and 0.9 mol of CF3SO3H and 0.006 mol of HAc and 0.45 mol of H2SO4 and 0.5 mol of CF3COOH, stir thoroughly; then add 0.01 mol of NaHSO3 and 0.01 mol of NaHSO4 and 0.01 mol of Na2S2O4, add water to make the solution 100 mL, and stir thoroughly, and the desired prepared electrolyte is obtained.

[0132] Example 14: Preparation of 100 mL of 0.02 M Eu Cl3 and 3.0 M Tm(CH3SO3)3 and 0.02 M Yb(CF3SO3)3 and 0.02 M Pr(CF3COO)3 and 3.0 M TbCl3 and 0.02 M Dy(CF3SO3)3 and 5.0 M CH3SO3H and 5.0 M CF3COOH and 0.1 M ZnCl2 and 0.1 M NaHSO3 and 0.1 M NaHSO4 and 0.1 M Na2S2O4 negative electrode electrolyte.

[0133] First, take 0.001 mol of Eu2O3 and 0.15 mol of Tm2O3 and 0.001 mol of Yb2O3 and 0.001 mol of Pr2(CO3)3 and 0.15 mol of Tb2(CO3)3 and 0.001 mol of Dy2(CO3)3, put them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.906 mol of HCl and 1.4 mol of CH3SO3H and 0.012 mol of CF3SO3H and 0.506 mol of CF3COOH, stir thoroughly; then add 0.01 mol of ZnCl2 and 0.01 mol of NaHSO3 and 0.01 mol of NaHSO4 and 0.01 mol of Na2S2O4, add water to make the solution 100 mL, and stir thoroughly, and the desired prepared electrolyte is obtained.

[0134] Example 15: Prepare 100mL of 3.0M SmCl3 and 0.01M Eu2(SO4)3 and 0.02M Tm(CH3SO3)3 and 3.0MYb(CF3SO3)3 and 3.0M CeAc3 and 0.02M Pr(CF3COO)3 and 0.02M TbCl3 and 1.5M Dy2(SO4)3 and 5.0MCH3SO3H and 5.0MCF3COOH negative electrode electrolyte.

[0135] First, weigh 0.15mol Sm2O3, 0.001mol Eu2O3, 0.001mol Tm2O3, 0.15mol Yb2O3, 0.15mol Ce2(CO3)3, 0.001mol Pr2(CO3)3, 0.001mol Tb2(CO3)3 and 0.15mol Dy2(CO3)3, put them in a 250mL beaker, add 30mL water and stir thoroughly; then add 0.906mol HCl, 0.453mol H2SO4, 0.506molCH3So3H, 0.9molCF3SO3H, 0.9mol HAc and 0.506mol CF3COOH and stir thoroughly; add water to make the solution 100mL, stir thoroughly to obtain the required electrolyte.

[0136] Example 16 : Prepare 100mL of 6.0M Ce(CH3SO3)3, 1.0M HNO3, 1.0M CH3SO3H, 1.0MCF3SO3H, 1.0M CF3COOH, 0.25% polyacrylamide and 0.25% polyacrylic acid positive electrolyte.

[0137] First, weigh 0.3 mol Ce2(CO3)3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HNO3, 1.9 mol CH3SO3H, 0.1 mol CF3SO3H, and 0.1 mol CF3COOH, and stir thoroughly; add 0.25 g of polyacrylamide and 0.25 g of polyacrylic acid, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0138] Example 17: Prepare 100 mL of 6.0 M Pr(CH 3 SO 3 ) 3 , 1.0 M HNO 3 , 1.0 M CH 3 SO 3 H , 1.0 M CF 3 SO 3 H , 1.0 M CF 3 COOH , 0.25% polyacrylamide , and 0.25% polyacrylic acid positive electrolyte.

[0139] First, weigh 0.3 mol Pr2(CO3)3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HNO3, 1.9 mol CH3SO3H, 0.1 mol CF3SO3H, and 0.1 mol CF3COOH, and stir thoroughly; add 0.25 g of polyacrylamide and 0.25 g of polyacrylic acid, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0140] Example 18: Prepare 100 mL of 6.0 M Tb(CH 3 SO 3 ) 3 , 1.0 M HNO 3 , 1.0 M CH 3 SO 3 H , 1.0 M CF 3 SO 3 H , 1.0 M CF 3 COOH , 0.25% polyacrylamide , and 0.25% polyacrylic acid positive electrolyte.

[0141] First, weigh 0.3 mol Tb2(CO3)3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HNO3, 1.9 mol CH3SO3H, 0.1 mol CF3SO3H, and 0.1 mol CF3COOH, and stir thoroughly; add 0.25 g of polyacrylamide and 0.25 g of polyacrylic acid, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0142] Example 19: Prepare 100 mL of 6.0 M Dy(CH 3 SO 3 ) 3 , 1.0 M HNO 3 , 1.0 M CH 3 SO 3 H , 1.0 M CF 3 SO 3 H , 1.0 M CF 3 COOH , 0.25% polyacrylamide , and 0.25% polyacrylic acid positive electrolyte.

[0143] First, weigh 0.3 mol Dy2(CO3)3, place it in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HNO3, 1.9 mol CH3SO3H, 0.1 mol CF3SO3H, and 0.1 mol CF3COOH, and stir thoroughly; add 0.25 g of polyacrylamide and 0.25 g of polyacrylic acid, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0144] Example 20: Prepare 100 mL of 3.0 M Ce(CH3SO3)3, 3.0 M Sm(CH3SO3)3, 1.0 M HNO3, 1.0 M CH3SO3H, 1.0 M CF3SO3H, 1.0 M CF3COOH, 0.25% polyacrylamide, and 0.25% polyacrylic acid positive electrolyte.

[0145] First, weigh 0.15 mol Ce2(CO3)3 and 0.15 mol Sm2O3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.1 mol HNO3, 1.9 mol CH3SO3H, 0.1 mol CF3SO3H, and 0.1 mol CF3COOH in sequence, and stir thoroughly; add 0.25 g of polyacrylamide and 0.25 g of polyacrylic acid, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0146] Example 21: Prepare 100 mL of 3.0 M Pr(CH 3 SO 3 ) 3 , 3.0 M Eu(CH 3 SO 3 ) 3 , 5.0 M HNO 3 and 0.25% polyacrylamide positive electrolyte.

[0147] First, weigh 0.15 mol Pr2(CO3)3 and 0.15 mol Eu2O3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.5 mol HNO3 and 1.8 mol CH3SO3H in sequence, stir thoroughly; add 0.25 g of polyacrylamide, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0148] Example 22: Prepare 100 mL of 3.0 M Tb(CH3SO3)3, 3.0 M Tm(CH3SO3)3, 10.0 M CF3SO3H and 0.25% polyacrylic acid positive electrolyte.

[0149] First, weigh 0.15 mol Tb2(CO3)3 and 0.15 mol Tm2O3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 1.8 mol CH3SO3H and 1.0 mol CF3SO3H in sequence, stir thoroughly; add 0.25 g of polyacrylic acid, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0150] Example 23: Prepare 100 mL of 3.0 M Dy(CH3SO3)3, 3.0 M Yb(CH3SO3)3, 3.0 M HNO3 and 0.25% polyacrylic acid positive electrolyte.

[0151] First, weigh 0.15 mol Dy2(CO3)3 and 0.15 mol Yb2O3, place them in a 250 mL beaker, add 30 mL of water, and stir thoroughly; then add 0.3 mol HNO3 and 1.8 mol CH3SO3H in sequence, stir thoroughly; add 0.25 g of polyacrylic acid, add water to the solution to 100 mL, and stir thoroughly to obtain the required electrolyte.

[0152] Example 24: Formulate 100 mL of 3.0 M Ce(CH3SO3)3and 3.0 M Pr(CF3SO3)3and 3.0 M Sm(CH3SO3)3and 3.0 M Eu(CF3SO3)3and 3.0 M HNO3and 0.5% polyacrylamide catholyte.

[0153] First, weigh 0.15 mol Ce2(CO3)3and 0.15 mol Pr2(CO3)3and 0.15 mol Sm2O3and 0.15 mol Eu2O3, put them in a 250 mL beaker, add 30 mL water, and stir well; then add 0.3 mol HNO3and 1.8 mol CH3SO3H and 1.8 mol CF3SO3H in turn, and stir well; add 0.5 g polyacrylamide, add water to 100 mL of solution, and stir well to obtain the desired formulated electrolyte.

[0154] Example 25: Formulate 100 mL of 3.0 M Tb(CH3SO3)3and 3.0 M Dy(CF3SO3)3and 3.0 M Tm(CH3SO3)3and 3.0 M Yb(CF3SO3)3and 3.0 M HNO3and 3.0 M CF3COOH and 0.5% polyacrylic acid catholyte.

[0155] First, weigh 0.15 mol Tb2(CO3)3and 0.15 mol Dy2(CO3)3and 0.15 mol Tm2O3and 0.15 mol Yb2O3, put them in a 250 mL beaker, add 30 mL water, and stir well; then add 0.3 mol HNO3and 1.8 mol CH3SO3H and 1.8 mol CF3SO3H and 0.3 mol CF3COOH in turn, and stir well; add 0.5 g polyacrylic acid, add water to 100 mL of solution, and stir well to obtain the desired formulated electrolyte.

[0156] Example 26: Formulate 100 mL of 1.0 M Ce(CH3SO3)3and 0.02 M Pr(CF3SO3)3and 1.0 M Tb(CF3SO3)3and 1.0 M Sm(CH3SO3)3and 0.02 M Eu(CF3SO3)3and 1.0 M Tm(CF3SO3)3and 2.0 M HNO3and 1.0 M CF3COOH catholyte.

[0157] First, weigh 0.05mol Ce2(CO3)3, 0.001mol Pr2(CO3)3, 0.05mol Tb2(CO3)3, 0.05mol Sm2O3, 0.001mol Eu2O3 and 0.05mol Tm2O3, put them in a 250mL beaker, add 30mL water and stir thoroughly; then add 0.2mol HNO3, 0.6mol CH3SO3H, 0.612mol CF3SO3H and 0.1mol CF3COOH in turn and stir thoroughly; add water to make the solution 100mL and stir thoroughly to obtain the required electrolyte.

[0158] Example 27: Prepare 100mL of 1.0M Ce(CH3SO3)3, 0.02M Pr(CF3SO3)3, 1.0M Dy(CF3SO3)3, 1.0M Sm(CH3SO3)3, 0.02M Eu(CF3SO3)3, 1.0M Yb(CF3SO3)3, 2.0M HNO3 and 2.0M CF3COOH positive electrolyte.

[0159] First, weigh 0.05mol Ce2(CO3)3, 0.001mol Pr2(CO3)3, 0.05mol Dy2(CO3)3, 0.05mol Sm2O3, 0.001mol Eu2O3 and 0.05mol Yb2O3, put them in a 250mL beaker, add 30mL water and stir thoroughly; then add 0.2mol HNO3, 0.6mol CH3SO3H, 0.612mol CF3SO3H and 0.2mol CF3COOH in turn and stir thoroughly; add water to make the solution 100mL and stir thoroughly to obtain the required electrolyte.

[0160] Example 28: Prepare 100mL of 3.0M Ce(CH3SO3)3 and 0.02M Tb(CF3SO3)3 and 3.0M Dy(CF3SO3)3 and 3.0M Sm(CH3SO3)3 and 0.02M Tm(CF3SO3)3 and 3.0M Yb(CF3SO3)3 and 1.0M HNO3 and 1.0M CH3SO3H and 1.0M CF3SO3H and 1.0M CF3COOH positive electrolyte.

[0161] First, weigh 0.15mol Ce2(CO3)3, 0.001mol Tb2(CO3)3, 0.15mol Dy2(CO3)3, 0.15mol Sm2O3, 0.001mol Tm2O3 and 0.15mol Yb2O3, put them in a 250mL beaker, add 30mL water and stir thoroughly; then add 0.1mol HNO3, 1.9mol CH3SO3H, 1.912mol CF3SO3H and 0.1mol CF3COOH in turn and stir thoroughly; add water to make the solution 100mL and stir thoroughly to obtain the required electrolyte.

[0162] Example 29: Prepare 100mL of 3.0M Pr(CH3SO3)3 and 0.02M Tb(CF3SO3)3 and 3.0M Dy(CF3SO3)3 and 3.0M Eu(CH3SO3)3 and 0.02M Tm(CF3SO3)3 and 3.0M Yb(CF3SO3)3 and 1.0M HNO3 and 1.0M CH3SO3H and 1.0M CF3SO3H and 1.0M CF3COOH positive electrolyte.

[0163] First, weigh 0.15mol Pr2(CO3)3, 0.001mol Tb2(CO3)3, 0.15mol Dy2(CO3)3, 0.15mol Eu2O3, 0.001mol Tm2O3 and 0.15mol Yb2O3, put them in a 250mL beaker, add 30mL water and stir thoroughly; then add 0.1mol HNO3, 1.9mol CH3SO3H, 1.912mol CF3SO3H and 0.1mol CF3COOH in turn and stir thoroughly; add water to make the solution 100mL and stir thoroughly to obtain the required electrolyte.

[0164] Example 30: Prepare 100mL of 3.0M Ce(CH3SO3)3 and 0.02M Pr(CH3SO3)3 and 0.02M Tb(CF3SO3)3 and 3.0M Dy(CF3SO3)3 and 3.0M Sm(CH3SO3)3 and 0.02M Eu(CH3SO3)3 and 0.02M Tm(CF3SO3)3 and 3.0MYb(CF3SO3)3 and 1.0M HNO3 and 1.0M CH3SO3H and 1.0M CF3SO3H and 1.0M CF3COOH positive electrolyte.

[0165] First, weigh 0.15mol Ce2(CO3)3, 0.001mol Pr2(CO3)3, 0.001mol Tb2(CO3)3, 0.15mol Dy2(CO3)3, 0.15mol Sm2O3, 0.001mol Eu2O3, 0.001mol Tm2O3 and 0.15mol Yb2O3, put them in a 250mL beaker, add 30mL water and stir thoroughly; then add 0.1mol HNO3, 1.912mol CH3SO3H, 1.912mol CF3SO3H and 0.1mol CF3COOH in turn and stir thoroughly; add water to make the solution 100mL and stir thoroughly to obtain the required electrolyte.

[0166] Example 31: Carbon felt was used as the positive and negative electrodes, and the apparent area of ​​both electrodes was 10 cm 2 The cation exchange membrane is used as the diaphragm. The negative electrolyte is 10 ml of 3.0 M EuCl3, 3.0 M Ce(CH3SO3)3, 5.0 M CF3SO3H, 1.0 M HAc, 0.1 M ZnCl2, 0.1 M NaHSO3, 0.1 M NaHSO4, and 0.1 M Na2S2O4 aqueous solution. The positive electrolyte is 10 ml of 3.0 M Eu(CH3SO3)3, 3.0 M Ce(NO3)3, 3.0 M HNO3, and 1.0 M CF3COOH aqueous solution. The charge and discharge current density is 100 mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 88.1%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.185 W / cm 2 , which is about 1.68 times the power density of the all-vanadium liquid flow battery at the same current density.

[0167] Example 32: Carbon felt was used as the positive and negative electrodes, and the apparent area of ​​both electrodes was 10 cm 2 The cation exchange membrane is the diaphragm. The negative electrolyte is 10ml of 6.0M SmCl3, 6.0M Pr(CH3SO3)3, 10M CF3SO3H, 2.0M HAc, 0.1MZnCl2, 0.1M NaHSO3, 0.1M NaHSO4, and 0.1M Na2S2O4 aqueous solution, and the positive electrolyte is 10ml of 6.0M Sm(CH3SO3)3, 6.0M Pr(NO3)3, 10M CF3SO3H, and 2.0M CF3COOH aqueous solution. The charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 84.9%, which is higher than the 75% energy efficiency of zinc-cerium flow battery; the power density is 0.183 W / cm2 , which is about 1.66 times the power density of the all-vanadium liquid flow battery at the same current density.

[0168] Example 33: Carbon felt was used as the positive and negative electrodes, and the apparent area of ​​both electrodes was 10 cm 2 The cation exchange membrane is the diaphragm. The negative electrolyte is 10ml of 1.0M TmCl3, 1.0M Tb(CH3SO3)3, 1.0M HCl, 1.0M CH3SO3H, 1.0M HAc, 0.1M ZnCl2, 0.1M NaHSO3, 0.1M NaHSO4, and 0.1M Na2S2O4 aqueous solution, and the positive electrolyte is 10ml of 1.0M Tm(CH3SO3)3, 1.0M Tb(NO3)3, 1.0M CH3SO3H, 1.0M HNO3, and 1.0M CF3COOH aqueous solution. The charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 86.3%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.181 W / cm 2 , which is about 1.64 times the power density of the all-vanadium liquid flow battery at the same current density.

[0169] Example 34: Carbon felt was used as the positive and negative electrodes, and the apparent area of ​​both electrodes was 10 cm 2 The cation exchange membrane is the diaphragm. The negative electrolyte is 10ml of 1.0M YbCl3, 1.0M Dy(CH3SO3)3, 1.0M HCl, 1.0M CH3SO3H, 1.0M HAc, 0.1M ZnCl2, 0.1M NaHSO3, 0.1M NaHSO4, and 0.1M Na2S2O4 aqueous solution, and the positive electrolyte is 10ml of 1.0M Yb(CH3SO3)3, 1.0M Dy(NO3)3, 1.0M CH3SO3H, 1.0M HNO3, and 1.0M CF3COOH aqueous solution. The charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 87.3%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.187 W / cm 2 , which is about 1.70 times the power density of the all-vanadium liquid flow battery at the same current density.

[0170] Example 35: Carbon felt was used as the positive and negative electrodes, and the apparent area of ​​both electrodes was 10 cm 2. The cation exchange membrane is the diaphragm. The negative electrode electrolyte is 10ml 1.0M SmCl3 and 1.0M EuCl3 and 1.0M Ce(CH3SO3)3 and 1.0M Pr(CH3SO3)3 and 3.0M HCl and 3.0M HAc and 0.1M ZnCl2 and 0.1M NaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 aqueous solution, the positive electrode electrolyte is 10ml 1.0M Sm(CH3SO3)3 and 1.0M Eu(CH3SO3)3 and 1.0M Ce(NO3)3 and 1.0M Pr(NO3)3 and 1.0M CH3SO3H and 3.0M HNO3 and 0.05% polyacrylamide and 0.5% polyacrylic acid aqueous solution, the charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 86.5%, which is higher than the 75% energy efficiency of zinc-cerium flow battery; the power density is 0.183 W / cm 2 , which is about 1.66 times the power density of the all-vanadium liquid flow battery at the same current density.

[0171] Example 36: Carbon felt was used as the positive and negative electrodes, and the apparent area of ​​both electrodes was 10 cm 2 . The cation exchange membrane is a diaphragm. The negative electrode electrolyte is 10 ml of 2.2M TmCl3 and 2.2M YbCl3 and 2.2M Tb(CH3SO3)3 and 2.2M Dy(CH3SO3)3 and 2.2M HCl and 2.2M CH3SO3H and 2.2M HAc and 0.1M ZnCl2 and 0.1M NaHSO3 and 0.1M NaHSO4 and 0.1MNa2S2O4 aqueous solution, the positive electrode electrolyte is 10 ml of 2.2M Tm(CH3SO3)3 and 2.2M Yb(CH3SO3)3 and 2.2M Tb(NO3)3 and 2.2M Dy(NO3)3 and 2.2M CH3SO3H and 2.2M HNO3 and 2.2M HCF3COOH and 0.05% polyacrylamide and 0.5% polyacrylic acid aqueous solution, and the charge and discharge current density is 100 mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 85.7%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.182 W / cm 2 , which is about 1.65 times the power density of the all-vanadium liquid flow battery at the same current density.

[0172] Example 37: Carbon felt was used as the positive and negative electrodes, both with an apparent area of ​​10 cm 2. The cation exchange membrane is a diaphragm. The negative electrode electrolyte is 10ml 1.8M SmCl3 and 1.8M YbCl3 and 1.8M Ce(CH3SO3)3 and 1.8M Dy(CH3SO3)3 and 1.8M HCl and 1.8M CH3SO3H and 1.8M HAc and 0.1M ZnCl2 and 0.1M NaHSo3 and 0.1M NaHSO4 and 0.1MNa2S2O4 aqueous solution, the positive electrode electrolyte is 10ml 1.8M Sm(CH3SO3)3 and 1.8M Yb(CH3SO3)3 and 1.8M Ce(NO3)3 and 1.8M Dy(NO3)3 and 1.8M CH3SO3H and 1.8M HNO3 and 1.8M HCF3COOH and 0.05% polyacrylamide and 0.25% polyacrylic acid aqueous solution, the charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 89.0%, which is higher than the 75% energy efficiency of zinc-cerium flow battery; the power density is 0.180 W / cm 2 , which is about 1.63 times the power density of all-vanadium redox flow batteries at the same current density. The battery's cycle life reaches 20,000 times, far exceeding the 200 cycles of zinc-cerium redox flow batteries.

[0173] Example 38: Carbon felt was used as the positive and negative electrodes, with an apparent area of ​​10 cm 2 . The cation exchange membrane is a diaphragm. The negative electrode electrolyte is 10ml 1.6MEuCl3 and 1.6M TmCl3 and 1.6M Pr(CH3SO3)3 and 1.6M Tb(CH3SO3)3 and 1.6MHCl and 1.6M CH3SO3H and 1.6M HAc and 0.1M ZnCl2 and 0.1M NaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 aqueous solution, the positive electrode electrolyte is 10ml 1.6M Eu(CH3SO3)3 and 1.6M Tm(CH3SO3)3 and 1.6M Pr(NO3)3 and 1.6MTb(NO3)3 and 1.6M CH3SO3H and 1.6M HNO3 and 1.6M HCF3COOH and 0.05% polyacrylamide and 0.05% polyacrylic acid aqueous solution, the charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 86.9%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.179 W / cm 2 , which is about 1.63 times the power density of the all-vanadium liquid flow battery at the same current density.

[0174] Example 39: Carbon felt was used as the positive and negative electrodes, with an apparent area of ​​10 cm2 . The cation exchange membrane is a diaphragm. The negative electrode electrolyte is 10ml 1.3MSmCl3 and 1.3MEuCl3 and 1.3M TmCl3 and 1.3M Ce(CH3SO3)3 and 1.3M Pr(CH3SO3)3 and 1.3M Tb(CH3SO3)3 and 1.3M HCl and 1.3M CH3SO3H and 1.3M HAc aqueous solution, the positive electrode electrolyte is 10ml 1.3M Sm(CH3SO3)3 and 1.3M Eu(CH3SO3)3 and 1.3M Tm(CH3SO3)3 and 1.3M Ce(NO3)3 and 1.3M Pr(NO3)3 and 1.3M Tb(NO3)3 and 1-3M CH3SO3H and 1.3M HNO3 and 1.3M HCF3COOH and 0.05% polyacrylamide and 0.35% polyacrylic acid aqueous solution, and the charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 83.2%, which is higher than the 75% energy efficiency of zinc-cerium flow battery; the power density is 0.188 W / cm 2 , which is about 1.71 times the power density of the all-vanadium liquid flow battery at the same current density.

[0175] Example 40: Carbon felt was used as the positive and negative electrodes, both with an apparent area of ​​10 cm 2 . The cation exchange membrane is a diaphragm. The negative electrolyte is 10ml 1.5MSmCl3 and 1.5MEuCl3 and 1.5M YbCl3 and 1.5M Ce(CH3SO3)3 and 1.5M Pr(CH3SO3)3 and 1.5M Dy(CH3SO3)3 and 1.5M HCl and 1.5M CH3SO3H and 1.5M HAc and 0.1M ZnCl2 and 0.1MNaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 aqueous solution, and the positive electrolyte is 10ml 1.5M Sm(CH3SO3)3 and 1.5MEu(CH3SO3)3 and 1.5M Yb(CH3SO3)3 and 1.5M Ce(NO3)3 and 1.5M Pr(NO3)3 and 1.5M Dy(NO3)3 and 1.5MCH3SO3H and 1.5M HNO3 and 1.5M HCF3COOH and 0.05% polyacrylamide and 0.45% polyacrylic acid aqueous solution, the charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 90.5%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.187 W / cm 2 , which is about 1.70 times the power density of the all-vanadium liquid flow battery at the same current density.

[0176] Example 41: Carbon felt was used as the positive and negative electrodes, both with an apparent area of ​​10 cm 2 . The cation exchange membrane is a diaphragm. The negative electrolyte is 10ml 1.1MSmCl3 and 1.1MTmCl3 and 1.1M YbCl3 and 1.1M Ce(CH3SO3)3 and 1.1M Tb(CH3SO3)3 and 1.1M Dy(CH3SO3)3 and 1.1M HCl and 1.1M CH3SO3H and 1.1M HAc and 0.1M ZnCl2 and 0.1MNaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 aqueous solution, and the positive electrolyte is 10ml1.1M Sm(CH3SO3)3 and 1.1MTm(CH3SO3)3 and 1.1M Yb(CH3SO3)3 and 1.1M Ce(NO3)3 and 1.1M Tb(NO3)3 and 1.1M Dy(NO3)3 and 1.1MCH3SO3H and 1.1M HNO3 and 1.1M HCF3COOH and 0.05% polyacrylamide water and 0.5% polyacrylic acid solution, the charge and discharge current density is 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 89.7%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.184 W / cm 2 , which is about 1.67 times the power density of the all-vanadium liquid flow battery at the same current density.

[0177] Example 42: Carbon felt was used as the positive and negative electrodes, with an apparent area of ​​10 cm 2 . The cation exchange membrane is a diaphragm. The negative electrolyte is 10ml 0.8MEuCl3 and 0.8MTmCl3 and 0.8M YbCl3 and 0.8M Pr(CH3SO3)3 and 0.8M Tb(CH3SO3)3 and 0.8M Dy(CH3SO3)3 and 1.0M HCl and 1.0M CH3SO3H and 1.0M HAc and 0.1M ZnCl2 and 0.1MNaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 aqueous solution, and the positive electrolyte is 10ml 0.8M Eu(CH3SO3)3 and 0.8MTm(CH3SO3)3 and 0.8M Yb(CH3SO3)3 and 0.8M Pr(NO3)3 and 1.0M Tb(NO3)3 and 0.8M Dy(NO3)3 and 1.0MCH3SO3H and 1.0M HNO3, 1.0M HCF3COOH and 0.05% polyacrylamide aqueous solution, charge and discharge current density is 100mA / cm 2The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 86.8%, which is higher than the 75% energy efficiency of zinc-cerium flow batteries; the power density is 0.189 W / cm 2 , which is about 1.72 times the power density of the all-vanadium liquid flow battery at the same current density.

[0178] Example 43: Carbon felt was used as the positive and negative electrodes, both with an apparent area of ​​10 cm 2 . The cation exchange membrane is a diaphragm. The negative electrode electrolyte is 10ml 0.5MSmCl3 and 0.5MEuCl3 and 0.5MTmCl3 and 0.5M YbCl3 and 0.5M Ce(CH3SO3)3 and 0.5M Pr(CH3SO3)3 and 0.5M Tb(CH3SO3)3 and 0.5M Dy(CH3SO3)3 and 1.0M HCl and 1.0M CH3SO3H and 1.0M HAc and 0.1M ZnCl2 and 0.1M NaHSO3 and 0.1M NaHSO4 and 0.1M Na2S2O4 aqueous solution, and the positive electrode electrolyte is 10ml 0.5M Sm(CH3SO3)3 and 0.5M Eu(CH3SO3)3 and 0.5M Tm(CH3SO3)3 and 0.5M Yb(CH3SO3)3 and 0.5MCe(NO3)3 and 0.5M Pr(NO3)3, 0.5M Tb(NO3)3, 0.5M Dy(NO3)3, 1.0M CH3SO3H, 1.0M HNO3, 1.0M HCF3COOH, and 0.05% polyacrylic acid aqueous solution, charge and discharge current density 100mA / cm 2 The electrolyte flow rate is 50 mL / min. The battery has an energy efficiency of 83.5%, which is higher than the 75% energy efficiency of zinc-cerium flow battery; the power density is 0.179 W / cm 2 , which is about 1.63 times the power density of the all-vanadium liquid flow battery at the same current density.

[0179] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. An electrolyte for a rare earth flow battery, characterized in that: include: A positive electrode electrolyte and a negative electrode electrolyte, wherein the active substance of the positive electrode electrolyte is selected from a first lanthanide metal element, and the active substance of the negative electrode electrolyte is selected from a second lanthanide metal element; When the first lanthanide metal element in the positive electrode electrolyte undergoes a charging electrochemical reaction, the valence of the first lanthanide metal element changes from trivalent to tetravalent, and when the discharge electrochemical reaction occurs, the valence of the first lanthanide metal element changes from tetravalent to trivalent; When the second lanthanide metal element in the negative electrode electrolyte undergoes a charging electrochemical reaction, the valence of the second lanthanide metal element changes from trivalent to divalent, and when the discharge electrochemical reaction occurs, the valence of the second lanthanide metal element changes from divalent to trivalent; The first lanthanide metal element is selected from at least one of Ce, Pr, Tb, and Dy; the second lanthanide metal element is selected from at least one of Sm, Eu, Tm, and Yb; The positive electrode electrolyte further comprises a second lanthanide metal element, and the concentration of each second lanthanide metal element is 0.02-6.0M; and / or, the negative electrode electrolyte further comprises a first lanthanide metal element, and the concentration of each first lanthanide metal element is 0.02-6.0M; The concentration of each first lanthanide metal element contained in the positive electrode electrolyte is 0.02-6.0M; The concentration of each second lanthanide metal element contained in the negative electrode electrolyte is 0.02-6.0M.

2. The electrolyte according to claim 1, characterized in that The positive electrode electrolyte comprises a first lanthanide metal element, a first type of acid, and 0-0.5 wt % polyacrylamide and / or 0-0.5 wt % polyacrylic acid; the hydrogen ion concentration in the positive electrode electrolyte is 0.02-10 M; The negative electrode electrolyte includes a second lanthanide metal element, a second acid, 0-0.25M zinc ions, 0-2.0M NaHSO3, 0-2.0M NaHSO4, and 0-2.0M Na2S2O4; the hydrogen ion concentration in the negative electrode electrolyte is 0.02-10M.

3. The method for preparing the positive electrolyte according to any one of claims 1 to 2, characterized in that: include: Step S1, weighing a salt of a first lanthanide metal and an oxide of a second lanthanide metal, and adding them to a certain amount of water; Step S2, adding the first type of acid to the solution obtained in step S1 and stirring thoroughly; optionally, further adding polyacrylamide and / or polyacrylic acid; Step S3: add the remaining amount of water to make up the volume.

4. The method for preparing the negative electrode electrolyte according to any one of claims 1 to 2, characterized in that: include: Step S1′, weighing the oxide of the second lanthanide metal and the salt of the first lanthanide metal, and adding them to a certain amount of water; Step S2', adding the second type of acid to the solution obtained in step S1' and stirring thoroughly; optionally, further adding at least one of zinc salt, NaHSO3, NaHSO4, and Na2S2O4; Step S3', adding the remaining amount of water to make up the volume.

5. The method according to claim 3 or 4, characterized in that The salt of the first lanthanide metal is a carbonate; the zinc salt is zinc chloride; the first type of acid is selected from at least one of nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid; the second type of acid is selected from at least one of hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and trifluoroacetic acid.

6. A rare earth flow battery, characterized in that: include: Anode, cathode electrolyte, cathode, cathode electrolyte and ion exchange membrane; The positive electrode electrolyte is the positive electrode electrolyte according to any one of claims 1 to 2, or the positive electrode electrolyte prepared by the method according to any one of claims 3 and 5; The negative electrode electrolyte is the negative electrode electrolyte according to any one of claims 1-2, or the negative electrode electrolyte prepared by the method according to any one of claims 4-5; The ion exchange membrane separates the battery cell into a positive electrode chamber and a negative electrode chamber, with the positive electrode in the positive electrode chamber and the negative electrode in the negative electrode chamber.

7. The rare earth flow battery according to claim 6, characterized in that Multiple rare earth flow battery cells are connected into a battery stack.

8. The battery according to any one of claims 6 to 7, characterized in that: The positive electrode electrolyte is placed in the positive electrode tank, and the positive electrode chamber is connected to the positive electrode tank and the first pump through a first electrolyte conduit to form a loop, and the positive electrode electrolyte circulates in the loop; The negative electrode electrolyte is placed in the negative electrode tank, and the negative electrode chamber is connected to the negative electrode tank and the second pump through a second electrolyte conduit to form a loop, and the negative electrode electrolyte circulates in the loop.

9. Application of the battery according to any one of claims 6 to 8 in the field of energy storage.

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