CN110034342A - Water system zinc-tellurium secondary battery - Google Patents
Water system zinc-tellurium secondary battery Download PDFInfo
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- CN110034342A CN110034342A CN201910359428.8A CN201910359428A CN110034342A CN 110034342 A CN110034342 A CN 110034342A CN 201910359428 A CN201910359428 A CN 201910359428A CN 110034342 A CN110034342 A CN 110034342A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the field of secondary batteries, and particularly relates to a zinc-tellurium-based water system secondary battery. An aqueous secondary battery, the positive electrode containing tellurium; the negative electrode contains zinc; and an aqueous electrolyte and a separator provided between the positive electrode and the negative electrode. The invention is mainly based on the energy storage mechanism of the oxidation-reduction reaction of the compound of the single substance tellurium and the four-valence tellurium (tellurium dioxide or tellurite) in the water system electrolyte at the anode and the dissolution (oxidation)/deposition (reduction) reaction of the zinc ions at the cathode, so the water system zinc-tellurium secondary battery has the advantages of high capacity, long cycle life, safety, environmental protection and the like, and can be widely applied to the important fields of consumer electronic equipment, intelligent devices, electric vehicles, communication, aerospace, large-scale energy storage and the like.
Description
Technical Field
The invention belongs to the field of secondary batteries, and particularly relates to a zinc-tellurium-based water system secondary battery.
Background
The increasingly severe situation of energy and environment situation brings great examination to human survival, and the new energy industry is accelerated to be cultivated and developed, so that the method is an urgent task of effectively relieving energy and environment pressure and promoting sustainable development, and is a strategic measure for accelerating transformation and upgrading of industry and cultivating new economic growth points and international competitive advantages. Lithium ion batteries have now largely monopolized the market share of consumer electronics batteries and are also marching towards more valuable electric vehicles. Unfortunately, however, lithium ion batteries have the problem of flammability and explosiveness due to their own electrochemical mechanism and limitation of materials used, which makes them unsatisfactory for many fields where safety and stability applications are emphasized, such as implant devices, large-scale energy storage, and special military applications. Although the energy density of the water-based battery is lower than that of the lithium ion battery, the higher safety of the water-based battery makes the water-based battery inevitably occupy a place in a future energy storage system. Although lead-acid battery systems are typical water-based batteries, mature in technology and low in cost, the problems of high pollution and high toxicity are in conflict with the future green development requirements of the country. Breaking the traditional mode, the development of a low-cost and high-performance water-based battery system based on new concepts and technologies is urgent.
As is well known, the zinc cathode integrates the advantages of low cost, large storage capacity, high volume specific capacity, high safety, high stability and the like, and occupies an irreplaceable position in the application of human electrochemical energy storage devices. Textbooks generally represent a human advance in electrochemical energy storage from the original voltaic stack, luxron Xie Dianchi, daniel cells to the widely used zinc-silver, zinc-air and zinc-manganese cell systems. With the continuous importance on the effective utilization of resources, green safety and environmental protection, the water-based zinc-based battery is on the stage of history again, and is actively concerned and reviewed by scientific research personnel. However, the electrochemical window of the aqueous electrolyte is narrow (1.23V), which limits the selection range of the anode of the aqueous zinc-based battery system and has very limited battery output voltage. However, the energy density of the energy storage device is not only dependent on the output voltage, but also has a direct relationship with the specific capacity of the system. Because the theoretical specific capacity of the metal zinc is higher (the specific capacity is 821mAh/g, and the specific capacity is 5862 mAh/g), the exploration of a novel high-capacity and high-stability anode material is very important for improving the energy density. Developed countries in the United states, english, japan, etc. have developed a great deal of early-stage exploratory applications in this field, and are relatively backward in China. The layout of a new system is carried out in advance, and the control points of the basic research on robbery and the industrial innovation are the key points for keeping the energy fight ahead in decades of the future in China.
In recent years, chalcogen elements such as oxygen, sulfur, selenium and tellurium have received great attention in the field of electrochemical energy storage, and particularly with the deep development of metal-oxygen, metal-sulfur batteries and other systems, the advantage of high capacity is fully embodied, and the energy density upper limit of electrochemical energy storage devices is expected to be impacted. The simple substances of sulfur, selenium and tellurium are solid, the valence states in corresponding compounds are very rich, the maximum valence state can reach +6, and the sulfur, selenium and tellurium have potential multi-electron transfer characteristics. Although the potential of the sulfur, selenium and tellurium compounds with negative valence states is lower, the potential interval with high valence states is expected to be suitable for an aqueous electrolyte system. If a reversible transition between valence states can be achieved, it is of great value for developing a high-capacity aqueous positive electrode material. Tellurium is more conductive (2X 10) than sulfur and selenium 2 S/m), the corresponding orthovalent compound is more stable (especially tellurium dioxide), provides the basis for a reversible electrochemical faradaic process, and is more suitable for application in aqueous zinc batteries. Tellurium-based positive electrode materials have been reported in lithium batteries (adv. Energy mater.2015,5,1401999, j. Mater.chem.a 2014,2, 12201), but mainly utilize an electrochemical process between tellurium (charged state) and lithium telluride (discharged state) in a negative valence interval, the mechanism is similar to that of a lithium-sulfur battery, and the corresponding reaction potential interval is far away from the potential window of an aqueous battery. The basic research on the electrochemical reaction of the tellurium-based compound in a water system is started in the last century, but the attention and the intensive research are not paid to the field of batteries, and at present, no report is made on the application of the electrochemical energy storage of the tellurium-based material in a positive valence state interval.
Disclosure of Invention
The purpose of the present invention is to provide a novel aqueous zinc-tellurium secondary battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
an aqueous zinc-tellurium secondary battery:
the positive electrode contains tellurium;
the negative electrode contains zinc; and
an aqueous electrolyte and a separator are provided between the positive electrode and the negative electrode (see fig. 1).
The positive electrode is a mixture containing tellurium and a positive current collector; wherein the tellurium-containing mixture is a tellurium active material, a conductive agent and a binder; according to the mass percentage, 30% -95% of tellurium active material, 3% -50% of conductive agent and 1% -30% of binder.
The tellurium active material is single substance tellurium, tellurium alloy, oxide of tellurium, sulfide of tellurium, tellurium selenium compound, tellurous acid (H) 2 TeO 3 ) One or more of tellurite, zinc telluride (ZnTe); the specific capacity of the tellurium active material is not less than 100mAh/g.
The tellurium alloy is an alloy material containing tellurium elements, wherein the content of the tellurium elements in the tellurium alloy is 0.005-95 wt%;
the chemical general formula of the tellurium oxide is Te x O y Wherein x and y respectively refer to the molar weight of Te and O in the oxide, namely one or a mixture of several oxides can exist; the ratio of x to y is 1.0;
the chemical general formula of the tellurium sulfide is Te x S y X and y respectively denote the molar weight of Te and S in sulfide, namely, the mixture of one or more sulfides (namely, alloy forms) can exist; wherein the ratio of x to y is 1.0-1.0;
the chemical general formula of the tellurium-selenium compound is Te x Se y X and y respectively denote the molar weight of Te and Se in the compound, namely one or a mixture of several compounds can exist; wherein the ratio of x to y is 1.000 to 0.005 to 1.000.
The tellurite is sodium tellurite (Na) 2 TeO 3 ) Potassium tellurite (K) 2 TeO 3 ) Barium hydrogen tellurate (Ba (HTeO) 3 ) 2 ) Barium tellurite (BaTeO) 3 ) Calcium tellurite (CateO) 3 ) Strontium tellurite (SrTeO) 3 ) Zinc tellurite (ZnTeO) 3 ) Copper tellurite (CuTeO) 3 ) Zinc hydrogen tellurate (Zn (HTeO) 3 ) 2 ) One or more of
Preferably, the tellurium active material is elemental tellurium, tellurium dioxide (TeO) 2 ) Tellurium-selenium compounds, zinc telluride; more preferably, the tellurium active material is elemental tellurium.
The water system electrolyte is a liquid or gel electrolyte containing water-soluble zinc salt, and the pH value range is 3-10; wherein the concentration of zinc ions in the aqueous electrolyte is between 0.01 and 10 mol/L.
The aqueous electrolyte also contains an additive; wherein the additive is one or more of surfactant, plating brightener, alcohol amine compound, compound obtained by condensing nitrogen heterocyclic compound and halogenated alcohol, and water-soluble polymer material with polar group.
The additive amount is 90-0% of the mass of the water-system electrolyte; the method improves the chemical stability of the zinc cathode and optimizes the electrochemical zinc deposition behavior, thereby improving the cycle performance.
Preferably, the aqueous electrolyte contains a water-soluble zinc salt. The water-soluble zinc salt is at least one or more of zinc sulfate, zinc nitrate and zinc alkylsulfonate. The concentration of zinc ions in the aqueous electrolyte is between 0.2 and 2 mol/L.
The water-soluble zinc salt is one or more of zinc sulfate, zinc nitrate, zinc acetate, zinc chloride, zinc fluoride, zinc citrate, zinc formate, zinc propionate, zinc acrylate, zinc benzoate, zinc hypochlorite, zinc chlorate, zinc perchlorate, zinc hexafluorophosphate and zinc alkylsulfonate.
The additive is one or more of a surfactant, an electroplating brightener, an alcohol amine compound, a compound formed by condensing a nitrogen heterocyclic compound and halogenated alcohol, and a water-soluble polymer material with polar groups, and the negative electrode is a zinc powder negative electrode or a porous, net-shaped or film material negative electrode made of pure metal zinc or zinc alloy.
The zinc powder negative electrode consists of a negative current collector and a zinc negative electrode mixture coated on the surface of the negative current collector; the zinc negative electrode mixture is made of a zinc active material, a conductive agent, a porous carbon material and a binder; wherein, the zinc active material is zinc powder and/or zinc alloy powder, and the addition amount is 20-90% of the mass of the zinc cathode mixture; the addition amount of the conductive agent is 5-50% of the mass of the zinc cathode mixture; the addition amount of the binder is 0-30% of the mass of the zinc cathode mixture. The addition amount of the porous carbon material is 0-40% of the mass of the zinc negative electrode mixture.
The conductive agent is one or more of free metal, carbon and conductive polymer.
The positive current collector and the negative current collector are porous, reticular and thin film materials made of one or more metals or alloys of carbon film, stainless steel, nickel, titanium, molybdenum, copper, antimony, aluminum, gold, silver and tin.
The invention has the advantages that:
the water system zinc-tellurium secondary battery utilizes the solid-phase electrochemical reaction between simple substance tellurium and quadrivalent tellurium compound and the energy storage mechanism of the deposition/dissolution of zinc ions, namely, in the water system electrolyte which has the pH value of 3-10 and contains the zinc ions, the negative pole takes zinc element as an active material to generate the zinc ions (Zn) 2+ ) And metal zinc, and the positive electrode takes simple substance tellurium or tellurium compound as active material to generate effective electrochemical solid-solid phase conversion reaction between simple substance tellurium and quadrivalent tellurium compound, the mechanism is as follows:
and (3) positive electrode:orNegative electrode:further, the battery of the present invention has high capacity and cycleThe performance is good.
As is well known, the theoretical specific capacity of the zinc cathode is up to 821mAh/g, but the capacities of the cathode materials matched with the zinc cathode are lower at present. Therefore, in an actual battery device, the specific capacity of the zinc negative electrode may not be sufficiently exhibited. Meanwhile, in view of the problem of limited potential window of the aqueous electrolyte, the energy density of the current zinc-based secondary battery still has no substantial breakthrough. The exploration of the high-capacity and high-stability cathode material is very critical. The energy storage mechanism of the tellurium anode provided by the invention is mainly an electrochemical reaction based on four-electron transfer, the theoretical specific capacity is up to 840mAh/g (elemental tellurium is taken as an active material), the theoretical capacity is equivalent to that of a zinc cathode, and the further improvement of the energy density can be realized. In addition, the electrochemical reaction of the tellurium anode is a solid phase transition process, the stability is high, and the high reversibility is realized, so that the battery device has long cycle performance. The water system zinc-tellurium secondary battery has the advantages of high capacity, simple process, environmental protection and the like, and can be used in the fields of implanted devices, flexible wearable electronic devices, large-scale static energy storage and other outstanding electrochemical energy storage.
Drawings
Fig. 1 is a schematic view of an aqueous zinc-tellurium secondary battery provided in an embodiment of the present invention.
Fig. 2 is a cyclic voltammogram of the aqueous zinc-tellurium secondary battery prepared in example 1 of the present invention.
FIG. 3 is a charge/discharge curve (calculated as mass of tellurium active material) at 50mA/g of the aqueous zinc-tellurium secondary battery prepared in example 1 of the present invention.
FIG. 4 is a graph showing the cycle performance (calculated on the tellurium active material mass) at 50mA/g of the aqueous zinc-tellurium secondary battery obtained in example 1 of the present invention.
FIG. 5 is a charge/discharge curve (calculated by mass of a tellurium active material) at 50mA/g of the aqueous zinc-tellurium secondary battery obtained in example 2 of the present invention.
FIG. 6 is a charge/discharge curve (calculated by mass of a tellurium active material) at 50mA/g of the aqueous zinc-tellurium secondary battery obtained in example 3 of the present invention.
FIG. 7 is the X-ray diffraction spectrum of the tellurium-selenium compound used in example 4 of the present invention.
FIG. 8 is a charge/discharge curve (calculated as the mass of the tellurium active material) at 50mA/g of the aqueous zinc-tellurium secondary battery obtained in example 4 of the present invention.
FIG. 9 is a charge/discharge curve (calculated as the mass of the tellurium active material) at 50mA/g of the aqueous zinc-tellurium secondary battery prepared in example 6 of the present invention.
FIG. 10 is a charge/discharge curve at 50mA/g of the aqueous zinc-tellurium secondary battery obtained in example 7 of the present invention.
FIG. 11 is a graph showing cycle performance (in terms of tellurium active material mass) at 50mA/g of the aqueous zinc-tellurium secondary battery obtained in example 7 of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The positive active material of the electrode takes simple substance tellurium or tellurium compound as the main material; the negative electrode mainly contains zinc element; the water-based electrolyte is a liquid or gel-state material which contains water-soluble zinc salt as a solute and water as a solvent and has ionic conductivity, and the pH value range is 3-10.
The solid-phase reaction of the secondary battery is based on the energy storage mechanism of the redox reaction of ions in the water system electrolyte and the compound (tellurium dioxide or tellurite) of simple substance tellurium and tetravalent tellurium at the positive electrode and the dissolution (oxidation)/deposition (reduction) reaction of zinc ions at the negative electrode, so that the water system zinc-tellurium secondary battery has the advantages of high capacity, long cycle life, safety, environmental protection and the like, and can be widely applied to important fields of consumer electronic equipment, intelligent devices, electric vehicles, communication, aerospace, large-scale energy storage and the like.
The current collectors adopted by the anode and the cathode are one of porous, reticular and thin film materials of one or more metals or alloys of carbon film, stainless steel, nickel, titanium, molybdenum, copper, antimony, aluminum, gold, silver and tin; the substance plays a role in supporting electrode materials and conducting electrons in the battery, and the substances can achieve corresponding characteristics, and titanium foil and stainless steel foil are taken as examples in the following embodiments.
Example 1
Electrolyte solution: 1mol/L zinc sulfate aqueous solution.
And (3) positive electrode: the method comprises the steps of adopting simple substance tellurium as a tellurium active material, mixing the tellurium active material, a conductive agent and a binder according to the mass ratio of 8. The conductive agent is conductive carbon black; the binder is polyvinylidene fluoride (PVDF).
Negative electrode: a zinc sheet having a thickness of 0.15 mm.
Assembling a positive electrode plate, a negative electrode, 1mol/L zinc sulfate aqueous solution and a diaphragm between the positive electrode and the negative electrode into a battery; a diaphragm: a fiberglass separator.
And (3) carrying out performance test on the assembled electrode:
as can be seen from fig. 2: the water system zinc-tellurium secondary battery has a pair of obvious redox peaks in a cyclic voltammetry curve at a scanning speed of 0.5 mV/s. The oxidation peak is between 1.2V and 1.4V and corresponds to the oxidation process from zero-valent tellurium to tetravalent tellurium in the anode and the electrodeposition process from zinc ions to metal zinc in the cathode; the reduction peak is located at 0.4V-0.6V and corresponds to the reduction process from quadrivalent tellurium to zero-valent tellurium in the positive electrode and the electrochemical dissolution process from metal zinc to zinc ions in the negative electrode.
As can be seen in fig. 3 and 4: the charge-discharge curve of the water system zinc-tellurium secondary battery under the condition of 50mA/g is stable, the discharge specific capacity of the second circle is 252mAh/g, the specific capacity after 20 cycles is 231mAh/g, and the specific capacity after 50 cycles is kept to be 176mAh/g. (specific capacity is calculated as mass of tellurium active material)
The simple substance tellurium in the embodiment is replaced by the tellurium alloy material, and the valence state of the tellurium in the substance is still 0, so that the similar effect of the embodiment 1 can be achieved.
Example 2
Electrolyte solution: 2mol/L zinc sulfate aqueous solution.
And (3) positive electrode: tellurium dioxide is used as a tellurium active material, the tellurium active material, a conductive agent and a binder are mixed according to the mass ratio of 6. The conductive agent is conductive carbon black; the binder is polyvinylidene fluoride (PVDF).
Negative electrode: a zinc sheet with a thickness of 0.15 mm;
assembling a battery by using a positive electrode plate, a negative electrode, 2mol/L zinc sulfate aqueous solution and a diaphragm between the positive electrode and the negative electrode; a diaphragm: a fiberglass separator.
And (3) carrying out performance test on the assembled electrode:
as can be seen from fig. 5: the charge and discharge behavior of the water system zinc-tellurium secondary battery under the condition of 50mA/g has an obvious activation process, the discharge specific capacity of the second circle is 202mAh/g, and the specific capacity after 20 cycles is 281mAh/g. (specific capacity is calculated as mass of tellurium active material)
In the above embodiment, the tellurium dioxide is replaced with another tellurium oxide material, a mixture of other tellurium oxide materials, or a tellurite, and the similar effect to that of embodiment 2 can be achieved due to the same performance and characteristics of the valence state of tellurium in the substance as tellurium dioxide.
Example 3
Electrolyte solution: 2mol/L of zinc trifluoromethanesulfonate.
And (3) positive electrode: the method is characterized in that simple substance tellurium is used as a tellurium active material, the tellurium active material, a conductive agent and a binder are mixed according to the mass ratio of 7. The conductive agent is conductive carbon black; the binder is sodium carboxymethylcellulose (CMC).
Negative electrode: the preparation method comprises the following steps of (1) mixing a zinc active material, a conductive agent, a porous carbon material and a binder according to the mass ratio of (6); the conductive agent is conductive carbon black; the binder is PVDF; the porous carbon material is activated carbon.
The battery is assembled by a positive electrode plate, a negative electrode plate, 2mol/L aqueous solution of zinc trifluoromethanesulfonate and a diaphragm between a positive electrode and a negative electrode, wherein the diaphragm is as follows: a hydrophilic Polyethylene (PE) nonwoven membrane.
And (3) carrying out performance test on the assembled electrode:
as can be seen from fig. 6: the charge and discharge behavior of the water system zinc-tellurium secondary battery in the embodiment 3 of the invention under the condition of 50mA/g has an obvious activation process, the specific discharge capacity of the second circle is 126mAh/g, and the specific discharge capacity after 20 cycles is 244mAh/g. (specific capacity is calculated as mass of tellurium active material)
From the above data and further increasing the concentration of zinc trifluoromethanesulfonate in the electrolyte, the solvation environment of zinc ions can be significantly changed, the hydrolysis effect of zinc ions can be reduced, and the stability of the negative electrode can be improved (conventional low-concentration zinc salt: (b) (b))<2 mol/L) of zinc ions and six water molecules form Zn- (H) 2 O) 6 The solvolysis layer of (2) causes the thermodynamics of a zinc cathode in the water system electrolyte to be unstable due to the hydrolysis of zinc ions), the content of free water in the electrolyte is greatly reduced along with the increase of the concentration, and corresponding hydrogen evolution and passivation side reactions are correspondingly inhibited.
Example 4
Electrolyte solution: 1mol/L zinc sulfate aqueous solution.
And (3) positive electrode: tellurium-selenium compound (TeSe) was used as the tellurium active material (see fig. 7). Mixing the tellurium active material, the conductive agent and the binder according to the mass ratio of 7. The conductive agent is conductive carbon black; the binder is PVDF.
Negative electrode: zinc sheet with thickness of 0.15mm
The battery is assembled by a positive electrode plate, a negative electrode, 1mol/L zinc sulfate aqueous solution and a diaphragm between the positive electrode and the negative electrode. A diaphragm: hydrophilic Polyethylene (PE) non-woven fabric diaphragm
The tellurium selenium compound (TeSe) is used as the tellurium selenium active material in the anode, and the XRD (X-ray diffraction) shown in figure 7 shows that the lattice spacing of the tellurium selenium compound is compromised relative to that of simple substance tellurium and simple substance selenium, and no other mixed phase interference exists. And (3) carrying out performance test on the assembled electrode:
as can be seen in fig. 8: the water system zinc-tellurium secondary battery has an overcharge phenomenon during the second circle charging under the condition of 50mA/g, the discharge specific capacity is 132mAh/g, and the specific capacity is stabilized at 125mAh/g after 20 cycles. (specific capacity is calculated as mass of tellurium active material)
Example 5
Electrolyte solution: 1mol/L zinc sulfate aqueous solution.
And (3) positive electrode: the sulfide of tellurium is used as the tellurium active material. And (3) mixing the tellurium active material, the conductive agent and the binder according to the mass ratio of 7. The conductive agent is conductive carbon black; the binder is PVDF.
Negative electrode: zinc sheet with thickness of 0.15mm
The battery is assembled by a positive electrode plate, a negative electrode, 1mol/L zinc sulfate aqueous solution and a diaphragm between the positive electrode and the negative electrode. A diaphragm: a hydrophilic Polyethylene (PE) nonwoven membrane.
And (3) carrying out performance test on the assembled electrode:
the water system zinc-tellurium secondary battery has an overcharge phenomenon during the second circle charging under the condition of 50mA/g, the specific discharge capacity is 156mAh/g, and the specific discharge capacity is stabilized at 141mAh/g after 20 cycles. (specific capacity is calculated as mass of tellurium active material)
Example 6
Electrolyte: 1mol/L zinc sulfate aqueous solution.
And (3) positive electrode: the method comprises the steps of taking zinc telluride as a tellurium active material, mixing the tellurium active material, a conductive agent and a binder according to the mass ratio of 7. The conductive agent is conductive carbon black; the binder is PVDF.
Negative electrode: zinc sheet with thickness of 0.15mm
The battery is assembled by a positive electrode plate, a negative electrode, 1mol/L zinc sulfate aqueous solution and a diaphragm between the positive electrode and the negative electrode. A diaphragm: a hydrophilic Polyethylene (PE) nonwoven membrane.
And (3) carrying out performance test on the assembled electrode:
as can be seen in fig. 9: the water system zinc-tellurium secondary battery has an overcharge phenomenon in the second circle of charging under the condition of 50mA/g, the specific discharge capacity is 108mAh/g, and the specific discharge capacity is increased to 117mAh/g after 5 times of circulation. (specific capacity is calculated as mass of tellurium active material)
Example 7
Electrolyte solution: 1mol/L zinc sulfate aqueous solution. The electrolyte contains the following additives: 0.5wt% cetyltrimethylammonium bromide (CTAB), 0.5wt% Sodium Dodecylbenzenesulfonate (SDBS), 1.0wt% polyethylene glycol (PEG).
And (3) positive electrode: the method is characterized in that simple substance tellurium is adopted as a tellurium active material, the tellurium active material, a conductive agent and a binder are mixed according to the mass ratio of 8. The conductive agent is conductive carbon black; the binder is PVDF.
Negative electrode: zinc sheet with thickness of 0.15mm
Assembling a battery by using a positive electrode plate, a negative electrode, electrolyte and a diaphragm between the positive electrode plate and the negative electrode plate; a diaphragm: a fiberglass separator.
And (3) carrying out performance test on the assembled electrode:
as can be seen from fig. 10: by adding the additive into the electrolyte, the discharge capacity of the water system zinc-tellurium secondary battery can be remarkably improved: the specific discharge capacity under the condition of 50mA/g can reach 420mAh/g, which is obviously higher than that of the anode material of the traditional zinc secondary battery. (specific capacity is calculated by mass of tellurium active material)
As can be seen from fig. 11: the water system zinc-tellurium secondary battery has excellent cycle stability, 76 percent of capacity is kept after 180 cycles, and the water system zinc-tellurium secondary battery is superior to the traditional zinc secondary battery.
Therefore, the water system zinc-tellurium secondary battery system provided by the invention has obvious advantages in the aspects of specific capacity and cycle performance, and has great application value.
Claims (10)
1. An aqueous zinc-tellurium secondary battery, characterized in that:
the positive electrode contains tellurium;
the negative electrode contains zinc; and
an aqueous electrolyte and a separator provided between the positive electrode and the negative electrode.
2. The aqueous zinc-tellurium secondary battery according to claim 1, characterized in that: the positive electrode is a mixture containing tellurium and a positive current collector; wherein the tellurium-containing mixture is a tellurium active material, a conductive agent and a binder; according to the mass percentage, 30-95% of tellurium active material, 3-50% of conductive agent and 1-30% of binder.
3. The aqueous zinc-tellurium secondary battery according to claim 2, characterized in that: the tellurium active material is single substance tellurium, tellurium alloy, oxide of tellurium, sulfide of tellurium, tellurium selenium compound, tellurous acid (H) 2 TeO 3 ) One or more of tellurite and zinc telluride (ZnTe); the specific capacity of the tellurium active material is not less than 100mAh/g.
4. The aqueous zinc-tellurium secondary battery according to claim 3, characterized in that: the tellurium alloy is an alloy material containing tellurium, wherein the content of the tellurium in the tellurium alloy is 0.005-95 wt%;
the chemical general formula of the tellurium oxide is Te x O y Wherein the ratio of x to y is 1.0 to 1.0.0；
The chemical general formula of the tellurium sulfide is Te x S y Wherein the ratio of x to y is 1.0 to 1.0;
the chemical general formula of the tellurium-selenium compound is Te x Se y Wherein the ratio of x to y is 1.000.
5. The aqueous zinc-tellurium secondary battery according to claim 3, characterized in that: the tellurite is sodium tellurite (Na) 2 TeO 3 ) Potassium tellurite (K) 2 TeO 3 ) Barium hydrogen tellurate (Ba (HTeO) 3 ) 2 ) Barium tellurite (BaTeO) 3 ) Calcium tellurite (CaTeO) 3 ) Strontium tellurite (SrTeO) 3 ) Zinc tellurite (ZnTeO) 3 ) Copper tellurite (CuTeO) 3 ) Zinc hydrogen tellurate (Zn (HTeO) 3 ) 2 ) One or more of (a).
6. The aqueous zinc-tellurium secondary battery according to claim 1, characterized in that: the water system electrolyte is a liquid or gel electrolyte containing water-soluble zinc salt, and the pH value range is 3-10; wherein the concentration of zinc ions in the aqueous electrolyte is between 0.01 and 10 mol/L.
7. The aqueous zinc-tellurium secondary battery according to claim 6, characterized in that: the aqueous electrolyte also contains an additive; wherein the additive is one or more of surfactant, plating brightener, alcohol amine compound, compound obtained by condensing nitrogen heterocyclic compound and halogenated alcohol, and water-soluble polymer material with polar group.
8. The aqueous zinc-tellurium secondary battery according to claim 7, characterized in that: the additive amount is 90% -0% of the mass of the water system electrolyte.
9. The aqueous zinc-tellurium secondary battery according to claim 1, characterized in that: the negative electrode is a zinc powder negative electrode or a porous, net-shaped or film material negative electrode made of pure metal zinc or zinc alloy.
10. The aqueous zinc-tellurium secondary battery according to claim 9, characterized in that: the zinc powder negative electrode consists of a negative current collector and a zinc negative electrode mixture coated on the surface of the negative current collector; the zinc negative electrode mixture is made of a zinc active material, a conductive agent, a porous carbon material and a binder; wherein, the zinc active material is zinc powder and/or zinc alloy powder, and the addition amount is 20-90% of the mass of the zinc cathode mixture; the addition amount of the conductive agent is 5-50% of the mass of the zinc cathode mixture; the addition amount of the binder is 0-30% of the mass of the zinc cathode mixture. The addition amount of the porous carbon material is 0-40% of the mass of the zinc negative electrode mixture.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112490515A (en) * | 2019-09-11 | 2021-03-12 | 中国科学院大连化学物理研究所 | Neutral zinc-manganese secondary battery and electrolyte |
| CN112670502A (en) * | 2021-01-28 | 2021-04-16 | 河南工业大学 | Antimony telluride nanosheet and application thereof in water-based zinc ion battery |
| CN115133109A (en) * | 2022-06-17 | 2022-09-30 | 苏州大学 | Water system copper ion battery |
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| US20050079415A1 (en) * | 2003-08-08 | 2005-04-14 | David Boone | Alkaline cells having high capacity |
| CN103872293A (en) * | 2014-03-18 | 2014-06-18 | 中国科学院化学研究所 | Novel lithium ion battery electrode material and application of lithium ion battery electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050079415A1 (en) * | 2003-08-08 | 2005-04-14 | David Boone | Alkaline cells having high capacity |
| CN103872293A (en) * | 2014-03-18 | 2014-06-18 | 中国科学院化学研究所 | Novel lithium ion battery electrode material and application of lithium ion battery electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112490515A (en) * | 2019-09-11 | 2021-03-12 | 中国科学院大连化学物理研究所 | Neutral zinc-manganese secondary battery and electrolyte |
| CN112490515B (en) * | 2019-09-11 | 2022-01-18 | 中国科学院大连化学物理研究所 | Neutral zinc-manganese secondary battery and electrolyte |
| CN112670502A (en) * | 2021-01-28 | 2021-04-16 | 河南工业大学 | Antimony telluride nanosheet and application thereof in water-based zinc ion battery |
| CN115133109A (en) * | 2022-06-17 | 2022-09-30 | 苏州大学 | Water system copper ion battery |
| CN115133109B (en) * | 2022-06-17 | 2023-05-12 | 苏州大学 | Water system copper ion battery |
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