CN106785242B - Chlorine lithium battery and energy storage method thereof - Google Patents
Chlorine lithium battery and energy storage method thereof Download PDFInfo
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- CN106785242B CN106785242B CN201611243195.8A CN201611243195A CN106785242B CN 106785242 B CN106785242 B CN 106785242B CN 201611243195 A CN201611243195 A CN 201611243195A CN 106785242 B CN106785242 B CN 106785242B
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- 238000004146 energy storage Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 title claims description 57
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 100
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003792 electrolyte Substances 0.000 claims abstract description 82
- 239000000460 chlorine Substances 0.000 claims abstract description 29
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 29
- 238000010248 power generation Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract 15
- 230000001105 regulatory effect Effects 0.000 claims description 17
- -1 carboxylic acid compounds Chemical class 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910007003 Li(C2F5SO2)2 Inorganic materials 0.000 claims description 4
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 claims description 4
- 229910007042 Li(CF3SO2)3 Inorganic materials 0.000 claims description 4
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 12
- 210000005056 cell body Anatomy 0.000 description 12
- 230000005611 electricity Effects 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
- H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
本发明提供一种氯锂电池及其储能方法，涉及电池技术领域。氯锂电池包括电池本体、氯气循环装置和电解液循环装置。电池本体包括壳体以及设置于壳体内并将壳体分隔成正极区域和负极区域的膜组件。壳体内设置有锂盐非水电解液。正极区域内设置有用于氯气反应的正极板。负极区域内设置有负极板。正极区域与氯气循环装置连通。负极区域与电解液循环装置连通。氯锂电池储能方法包括：将发电装置与氯锂电池电连接并向氯锂电池内输入电解液，将产生的氯气收集以备于循环利用。本氯锂电池属于大型储电装置，主要用于间歇性发电装置的储电设备或电站。通过氯气循环装置和电解液循环装置能够将氯锂电池工作过程产生的氯气和电解液收集以备于循环利用。
The present invention provides a lithium chloride battery and an energy storage method thereof, and relates to the technical field of batteries. The lithium chloride battery comprises a battery body, a chlorine gas circulation device and an electrolyte circulation device. The battery body comprises a shell and a membrane assembly arranged in the shell and dividing the shell into a positive electrode region and a negative electrode region. A lithium salt non-aqueous electrolyte is arranged in the shell. A positive electrode plate for chlorine reaction is arranged in the positive electrode region. A negative electrode plate is arranged in the negative electrode region. The positive electrode region is connected to the chlorine gas circulation device. The negative electrode region is connected to the electrolyte circulation device. The lithium chloride battery energy storage method comprises: electrically connecting a power generation device to the lithium chloride battery and inputting electrolyte into the lithium chloride battery, and collecting the generated chlorine for recycling. The lithium chloride battery belongs to a large-scale power storage device, and is mainly used for power storage equipment or power stations of intermittent power generation devices. The chlorine gas and electrolyte generated during the working process of the lithium chloride battery can be collected for recycling through the chlorine gas circulation device and the electrolyte circulation device.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a chlorine lithium battery and an energy storage method thereof.
Background
Electric energy as the most important secondary energy makes important contribution to the development and progress of human society. Electric energy is mainly obtained by converting other primary energy sources, so that the crisis of the primary energy sources directly influences the stable supply of the electric energy. In China, economic loss caused by switching off and limiting electricity during peak load of electricity utilization is hardly estimated every year, and meanwhile, the problem of environmental pollution caused by traditional thermal power generation is not ignored.
At present, the production and consumption of electricity occur almost simultaneously. The problems of electric energy shortage and environmental deterioration become two major problems restricting the sustainable development of national economy in China. How to conveniently and economically store electric power is still a difficult problem which puzzles scientists, and people cannot realize large-scale electric energy storage at present, so that the research on an advanced electric energy storage technology to realize energy-saving use has important theoretical research significance and practical value.
In the existing battery energy storage equipment, although great breakthrough is made in the aspects of safety performance, conversion efficiency, economic performance and the like, the conditions of industrial application are becoming mature. However, there are also problems in current battery energy storage, such as: a lead-acid battery: low energy density, short cycle life, easy pollution to the environment in the manufacturing process and the like; nickel-cadmium cell: the material has memory effect during long-term shallow charge and discharge, the price of cadmium material is expensive and the environment is seriously polluted, so the safe use and recovery are required; nickel-metal hydride batteries: greater self-discharge and lower cycle life; a lithium ion battery: has the problem of high cost; sodium-sulfur battery: has certain potential safety hazard and higher cost at present, so the application scale is still required to be further excavated.
Therefore, the above battery energy storage device is difficult to be directly applied to energy storage of a power generation device, and a solution is urgently needed to solve the problem.
Disclosure of Invention
The invention aims to provide a chlorine lithium battery which can be matched with a power generation device for use, and solves the problems that the power storage technology aims at achieving the goal of sustainable development of a power grid, the power supply and demand imbalance contradiction of electric quantity is solved, the power supply reliability is improved, and the like.
Another object of the present invention is to provide an energy storage method for a lithium chloride battery, which can store electric energy by using the lithium chloride battery.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a chlorine lithium battery which comprises a battery body, a chlorine circulating device for storing chlorine and an electrolyte circulating device for storing electrolyte. The battery body comprises a shell and a membrane assembly arranged in the shell and used for dividing the shell into a positive electrode area and a negative electrode area. A lithium salt non-aqueous electrolyte is arranged in the shell. A positive plate for chlorine reaction is arranged in the positive electrode area. And a negative plate is arranged in the negative region. The anode region is in communication with a chlorine gas circulation device. The negative electrode region is in communication with an electrolyte circulation device.
The invention provides an energy storage method of a chlorine lithium battery, which comprises the following steps: and electrically connecting the power generation device with the chlorine lithium battery, inputting electrolyte into the chlorine lithium battery, and collecting the generated chlorine for cyclic utilization.
The invention has the beneficial effects that: the chlorine lithium battery belongs to a large-scale electricity storage device and is mainly used for electricity storage equipment or a power station of an intermittent power generation device. Has the characteristics of simple structure, easy manufacture and the like. The positive pole region of chlorine lithium cell feeds the intercommunication with the chlorine circulation, and the negative pole region feeds through with electrolyte circulating device for chlorine that produces when chlorine lithium cell stored the electric energy can be collected and in order to be prepared for cyclic utilization when chlorine lithium cell output electric energy via chlorine circulating device, simultaneously, the electrolyte that produces when making chlorine lithium cell output electric energy collects and in order to be prepared for cyclic utilization when chlorine lithium cell stores the electric energy via electrolyte circulating device. The chlorine lithium battery is matched with the intermittent discovery device for use, can realize stable energy storage of a large-scale intermittent power generation device, can improve the economy, safety and reliability of a power grid, accords with the utilization and development of new energy resources advocated vigorously by the nation at present, and has remarkable economic and social benefits.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic structural diagram of a lithium chloride battery provided in an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a chlorine gas circulation device according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of an electrolyte circulation device according to an embodiment of the present invention.
Icon: 100-chlorine lithium battery; 110-a battery body; 111-a housing; 112-a membrane module; 113-a positive plate; 114-negative plate; 115-an adhesion layer; 116-positive electrode region; 117 — negative electrode region; 120-a chlorine gas circulation unit; 121-a chlorine gas recycle tank; 122-a source of chlorine gas; 123-an absorbing mechanism; 124-a first conduit; 125-a second conduit; 126-first regulating valve; 127-a second regulating valve; 128-third regulating valve; 130-electrolyte circulation means; 131-an electrolyte circulation tank; 132-a liquid inlet; 133-a liquid outlet; 134-a third conduit; 135-a fourth conduit; 136-a fourth regulating valve; 137-fifth regulating valve; 138-circulation pump.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The lithium chloride battery 100 and the energy storage method thereof according to the embodiment of the invention are described in detail below.
Referring to fig. 1, a lithium chloride battery 100 provided in this embodiment includes a battery body 110, a chlorine gas circulating device 120, and an electrolyte circulating device 130.
Referring to fig. 2, the battery body 110 includes a case 111, a membrane assembly 112, a positive electrode plate 113, and a negative electrode plate 114. The housing 111 has a closed structure similar to a rectangular parallelepiped. The membrane module 112 is disposed inside the casing 111, and the membrane module 112 partitions the inside of the casing 111 to form a positive electrode region 116 and a negative electrode region 117 which are disposed to face each other. Disposed within positive electrode region 116 is positive plate 113 for the reaction of chlorine gas, i.e., it is understood that chlorine gas and positive plate 113 comprise the positive electrode of the cell and may be referred to as a chlorine gas electrode. The negative electrode region 117 is provided with the negative electrode plate 114, i.e., the negative electrode plate 114 is understood to be the negative electrode of the battery body 110. An electrolyte is provided inside case 111, and membrane module 112, positive electrode plate 113, and negative electrode plate 114 are immersed in the electrolyte. Preferably, the positive electrode plate 113 and the negative electrode plate 114 are both plate-shaped structures, and the contact area between the electrolyte and the positive electrode plate 113 and the negative electrode plate 114 can be increased by providing the positive electrode plate 113 and the negative electrode plate 114 with the plate-shaped structures, thereby ensuring stable and continuous reaction inside the lithium chloride battery 100.
when the lithium chloride battery 100 stores electric energy, the reaction mechanism of the positive electrode is as follows:
2Cl-→Cl2+2e；
when the lithium chloride battery 100 outputs electric energy, the reaction mechanism of the positive electrode is as follows:
Cl2+2e→2Cl-。
the negative electrode plate 114 is selected from electrode plates made of at least one of graphite, copper foil, iron and aluminum, that is, the negative electrode plate 114 can be selected from one of the materials, and can also be selected from any mixture of a plurality of the materials. The present embodiment is not limited to the electrode plate material of the negative electrode plate 114, as long as the electrode plate material of the negative electrode plate 114 does not react with the electrolyte. The negative electrode plate 114 serves as a negative electrode of the lithium chloride battery 100, and the reaction occurs as follows:
when the lithium chloride battery 100 stores electric energy, the reaction mechanism of the positive electrode is as follows:
Li++e→Li；
when the lithium chloride battery 100 outputs electric energy, the reaction mechanism of the positive electrode is as follows:
Li→Li++e。
in the lithium chloride battery 100, lithium generated from the electrolyte may be accumulated in the negative electrode plate 114 and form the adhesion layer 115 during the storage of electric energy. Due to the use of the negative electrode plate 114 having a plate-like structure, rapid and uniform lithium accumulation in the negative electrode plate 114 can be achieved, i.e., the adhesion layer 115 is a uniformly distributed lithium metal layer, which ensures stable and continuous reaction inside the lithium chloride battery 100. In the process of outputting electric energy from the lithium chloride battery 100, the lithium metal adhesion layer 115 attached to the negative electrode plate 114 can react with the electrolyte, and the lithium chloride battery 100 finishes discharging, and the adhesion layer 115 completely reacts with the electrolyte.
The electrolyte includes a lithium salt and an organic solvent. The lithium salt may be selected from LiCl, LiCl and LiClO4、LiPF6、LiBF4、LiAsF6、Li(CF3CO2)2N、LiCF3SO3、Li(CF3SO2)3、Li(CF3SO2)2N、Li(C2F5SO2)2N、LiB(C2O4)2A mixture of at least one of the above. LiCl is used as a raw material or a product of main reaction of the positive electrode and the negative electrode and is an essential component of the electrolyte; and LiClO4、LiPF6、LiBF4、LiAsF6、Li(CF3CO2)2N、LiCF3SO3、Li(CF3SO2)3、Li(CF3SO2)2N、Li(C2F5SO2)2N、LiB(C2O4)2The lithium chloride ion battery is widely applied to conventional lithium batteries, has better solubility, stability and conductivity in an organic solvent, and can further provide lithium ions for the lithium chloride battery 100 so as to ensure the electricity storage performance of the lithium chloride battery 100.
The organic solvent is at least one selected from the group consisting of carbonate compounds, carboxylic acid compounds, ether compounds and nitrile compounds. Wherein the carbonate compound is selected from at least one of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; the carboxylic acid compound is at least one selected from melamine formaldehyde resin, methyl acrylate, ethyl acrylate and gamma-butyrolactone; the ether compound is at least one selected from tetrahydrofuran, 2-methyl-tetrahydrofuran and dimethoxymethane; the nitrile compound is selected from the group consisting of fluorodinitriles.
Referring to fig. 1 and 2, the chlorine gas circulation device 120 includes a chlorine gas circulation tank 121, a chlorine gas source 122, and an absorption mechanism 123. The positive region 116 of the cell body 110, the chlorine source 122, and the absorbing mechanism 123 are all in communication with the chlorine recycle tank 121. Specifically, the pipe for communicating between the chlorine gas circulation tank 121 and the positive electrode region 116 includes a first pipe 124 and a second pipe 125, both ends of the first pipe 124 are respectively communicated with the chlorine gas circulation tank 121 and the case 111 located at the bottom of the positive electrode region 116, and both ends of the second pipe 125 are respectively communicated with the chlorine gas circulation tank 121 and the case 111 located at the upper portion of the positive electrode region 116. That is, first duct 124 is located at a lower portion of positive electrode plate 113, and second duct 125 is located at an upper portion of positive electrode plate 113. The second pipe 125 serves to discharge chlorine gas to the outside of the cell body 110. When the chlorine lithium battery 100 stores electric energy, chlorine gas generated in the battery body 110 is collected at the top thereof and is input into the chlorine gas circulation tank 121 through the second pipe 125. The first pipe 124 is used to input chlorine into the inner cell body 110. When the chlorine lithium battery 100 outputs electric power, chlorine gas collected in the chlorine gas circulation tank 121 is input into the battery body 110 through the first pipe 124. The chlorine gas can diffuse from the bottom to the top in the cell body 110, which helps the diffusion of the chlorine gas to be uniform to ensure the reaction is sufficient.
In order to balance the pressure between the chlorine gas circulation tank 121 and the cell body 110, a regulating valve is provided to communicate the pipe between the circulation tank and the cell body 110. Specifically, the first pipe 124 is provided with a first regulating valve 126, and the second pipe 125 is provided with a second regulating valve 127. Preferably, the first and second control valves 126 and 127 are self-operated pressure control valves. Through such an arrangement, the pressure and flow rate of the chlorine gas can be controlled and adjusted, avoiding damage to the cell body 110.
In order to reduce the storage volume of chlorine gas, the chlorine gas circulation tank 121 is selected as a pressure tank. When the chlorine lithium battery 100 stores electric energy, the generated chlorine gas enters the pressure tank through the first pipeline 124, and the pressure tank is pressurized to convert the chlorine gas in the pressure tank into liquid chlorine, so that the storage volume of the chlorine gas is reduced.
In the circulation process of the chlorine lithium battery 100, the electrolyte and the chlorine gas in the chlorine lithium battery are gradually consumed, and in order to ensure that the service life of the chlorine lithium battery 100 is prolonged, the chlorine gas circulation tank 121 is communicated with the chlorine gas source 122. Chlorine gas is supplemented into the chlorine gas circulation tank 121 through the chlorine gas source 122, so that on one hand, air in the chlorine gas circulation tank 121 can be exhausted; on the other hand, chlorine gas can be supplemented into the chlorine gas circulation tank 121 through the chlorine gas source 122, so as to ensure that the chlorine lithium battery 100 can continuously and stably supply power.
The chlorine gas circulation tank 121 is communicated with the absorption mechanism 123. When the chlorine gas is injected into the chlorine gas circulation tank 121, the air in the chlorine gas circulation tank needs to be discharged. The air inside the chlorine gas circulation tank 121 carries a part of the chlorine gas when it is discharged, and therefore, the gas needs to be treated by the absorption mechanism 123 before being discharged into the air. The absorption mechanism 123 can be an absorption tower or an absorption tank as long as it can be filled with alkali liquor to absorb chlorine. Further, a pipe communicating between the absorption mechanism 123 and the chlorine gas circulation tank 121 is provided with a third regulating valve 128. Preferably, the third adjusting valve 128 is a check valve, which can effectively prevent the alkali solution and air inside the absorption mechanism 123 from entering the chlorine gas circulation tank 121, thereby avoiding damage to the lithium chloride battery 100 or influence on the energy storage efficiency.
Referring to fig. 1 and 3, the electrolyte circulation device 130 includes an electrolyte circulation tank 131 and a circulation pump 138. The negative electrode region 117 of the battery body 110 communicates with the electrolyte circulation tank 131. Specifically, the piping that communicates the electrolyte circulation tank 131 with the negative electrode region 117 includes a third piping 134 and a fourth piping 135. Both ends of the third pipe 134 are respectively communicated with the electrolyte circulation tank 131 and the case 111 at the top of the negative electrode region 117, and both ends of the fourth pipe 135 are respectively communicated with the chlorine gas circulation tank 121 and the case 111 at the bottom of the negative electrode region 117. That is, the third pipe 134 is positioned at the upper portion of the negative electrode plate 114, and the fourth pipe 135 is positioned at the lower portion of the negative electrode plate 114. The third pipe 134 is used to input the electrolyte to the inside of the battery body 110, and the third pipe 134 is provided with a circulation pump 138 and a fourth regulation valve 136. When the chlorine lithium battery 100 stores electric energy, the electrolyte inside the electrolyte circulation tank 131 is input to the negative electrode region 117 of the battery body 110 by the circulation pump 138, and the electrolyte participates in the reaction to generate chlorine gas. The fourth pipe 135 is used to discharge the electrolyte to the outside of the battery body 110, and the fourth pipe 135 is provided with a fifth regulating valve 137. When the chlorine lithium battery 100 outputs electric power, the electrolyte generated in the battery body 110 enters the electrolyte circulation tank 131 through the fourth pipe 135. Preferably, the fourth and fifth control valves 136 and 137 are self-operated pressure control valves. Through such an arrangement, the pressure and flow rate of the electrolyte can be controlled and adjusted, avoiding damage to the battery body 110.
Preferably, the electrolyte circulation tank 131 is provided with a liquid inlet 132 and a liquid outlet 133. Through inlet 132, can supply new electrolyte in the electrolyte circulation tank 131, through setting up liquid outlet 133, can discharge the too much useless electrolyte of circulation number in the electrolyte circulation tank 131. The service life of the chlorine lithium battery 100 can be increased by discharging the waste electrolyte and replenishing the new electrolyte.
In the using process, a plurality of battery bodies 110 can be arranged in series and placed in the battery placing bin and the battery container, so that the battery placing bin and the battery container have larger capacity, and the battery placing bin and the battery container are suitable for being matched with large-scale power generation devices.
An energy storage method of a chlorine lithium battery comprises the following steps:
the power generation device is electrically connected with the chlorine lithium battery 100, electrolyte is input into the chlorine lithium battery 100, and the generated chlorine gas is collected for recycling.
Because the solar energy, the wind energy or the water energy and other energy sources are adopted for generating electricity, the generated electric energy has intermittence because the energy sources have uncertainty. Therefore, it is necessary to store the generated electric energy in the lithium chloride battery 100 and then output the electric energy to the outside using the lithium chloride battery 100. The method comprises the following specific steps:
(1) and a power generation device such as a solar power generation device, a wind power generation device or a hydro power generation device is electrically connected to the positive electrode plate 113 and the negative electrode plate 114 of the battery body 110 of the chlorine lithium battery 100, and electric energy generated by the solar power generation device, the wind power generation device or the hydro power generation device is stored in the chlorine lithium battery 100.
(2) The circulation pump 138 and the fourth adjustment valve 136 are opened, and the electrolyte in the electrolyte circulation tank 131 is introduced into the battery body 110, so that the reaction occurs in the battery body 110 and chlorine gas is generated. When the second regulating valve 127 is opened, chlorine gas generated in the cell body 110 is sent to the chlorine gas circulation tank 121 through the second pipe 125.
(3) The chlorine gas entering the chlorine gas circulation tank 121 is pressurized and converted into liquid chlorine for recycling when the chlorine lithium battery 100 outputs electric energy, i.e., the electric energy of the chlorine lithium battery 100 is stored.
When the chlorine lithium battery 100 outputs electric energy, the load circuit is only required to be electrically connected with the positive plate 113 and the negative plate 114, the first regulating valve 126 and the fifth regulating valve 137 are opened, chlorine in the chlorine circulating tank 121 is conveyed into the battery body 110 through the first pipeline 124 and reacts in the battery body 110 to generate electrolyte, and the electrolyte enters the electrolyte circulating tank 131 through the fourth pipeline 135 to be recycled, so that the chlorine lithium battery 100 outputs electric energy.
The lithium chloride battery 100 of the present invention belongs to a large-sized power storage device, and is mainly used for a power storage facility or a power station of an intermittent power generation device. Has the characteristics of simple structure, easy manufacture and the like. The positive electrode area 116 of the chlorine lithium battery 100 is communicated with the chlorine gas circulating device 120, and the negative electrode area 117 is communicated with the electrolyte circulating device 130, so that chlorine gas generated when the chlorine lithium battery 100 stores electric energy can be collected by the chlorine gas circulating device 120 and is ready for cyclic utilization when the chlorine lithium battery 100 outputs electric energy, and meanwhile, electrolyte generated when the chlorine lithium battery 100 outputs electric energy is collected by the electrolyte circulating device 130 and is ready for cyclic utilization when the chlorine lithium battery 100 stores electric energy. The method has the characteristics of large capacity, high efficiency, high density and the like, can improve the economy, safety and reliability of the power grid, accords with the utilization and development of new energy resources vigorously advocated by the nation at present, and has remarkable economic and social benefits.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Preparing an electrolyte: LiCl, ethylene carbonate and fluorodinitrile are uniformly mixed to prepare the electrolyte.
Preparation of negative plate 114: the copper foil is rolled to produce the negative plate 114.
Assembling the chlorine lithium battery 100: the positive electrode plate 113 made of graphite, the negative electrode plate 114 prepared in the above-described step, and the membrane module 112 are enclosed in the case 111, and assembled into the battery body 110. An electrolyte is injected into the battery body 110 under an inert gas atmosphere and sealed. The assembled plurality of battery bodies 110 are connected in series and then mounted in a battery container, and the positive electrode region 116 of each battery body 110 is communicated with the chlorine gas circulation device 120. The negative electrode region 117 of each cell body 110 is communicated with the electrolyte circulation means 130.
A lithium chloride battery 100 is used in conjunction with a hydro-power generation device and supplies power to a load circuit.
Example 2
Preparing an electrolyte: LiCl and LiPF are added6、LiBF4Diethyl carbonate, methyl ethyl carbonate and 2-methyl-tetrahydrofuran are mixed evenly to prepare the electrolyte.
Preparation of negative plate 114: the negative plate 114 is made from iron and aluminum by cold pressing and rolling.
Assembling the chlorine lithium battery 100: the positive electrode plate 113 made of platinum, the negative electrode plate 114 prepared in the above step, and the membrane module 112 are enclosed in a case 111, and assembled into a battery body 110. An electrolyte is injected into the battery body 110 under an inert gas atmosphere and sealed. The assembled plurality of battery bodies 110 are connected in series and then mounted in a battery container, and the positive electrode region 116 of each battery body 110 is communicated with the chlorine gas circulation device 120. The negative electrode region 117 of each cell body 110 is communicated with the electrolyte circulation means 130.
The chlorine lithium battery 100 is used in combination with a solar power generation apparatus and a wind power generation apparatus and supplies power to a load circuit.
Example 3
Preparing an electrolyte: mixing LiCl and LiClO4、Li(CF3CO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2N、LiB(C2O4)2The propylene carbonate, the butylene carbonate, the dimethyl carbonate, the diethyl carbonate, the gamma-butyrolactone and the dimethoxymethane are uniformly mixed to prepare the electrolyte.
Preparation of negative plate 114: copper and aluminum are cold pressed and rolled to produce the negative plate 114.
Assembling the chlorine lithium battery 100: the positive electrode plate 113 made of platinum, the negative electrode plate 114 prepared in the above step, and the membrane module 112 are enclosed in a case 111, and assembled into a battery body 110. An electrolyte is injected into the battery body 110 under an inert gas atmosphere and sealed. The assembled plurality of battery bodies 110 are connected in series and then mounted in a battery container, and the positive electrode region 116 of each battery body 110 is communicated with the chlorine gas circulation device 120. The negative electrode region 117 of each cell body 110 is communicated with the electrolyte circulation means 130.
The lithium chloride battery 100 is used in combination with a wind power generation apparatus and supplies power to a load circuit.
Example 4
Preparing an electrolyte: mixing LiCl and LiClO4、LiPF6、LiBF4、LiAsF6、Li(CF3CO2)2N、LiCF3SO3、Li(CF3SO2)3、LiB(C2O4)2Tetrahydrofuran, 2-methyl-tetrahydrofuran and fluoro dinitrile are mixed homogeneously to produce the electrolyte.
Preparation of negative plate 114: the negative electrode plate 114 is manufactured by uniformly mixing molten copper and molten iron and rolling the mixture.
Assembling the chlorine lithium battery 100: the positive electrode plate 113 made of graphite, the negative electrode plate 114 prepared in the above-described step, and the membrane module 112 are enclosed in the case 111, and assembled into the battery body 110. An electrolyte is injected into the battery body 110 under an inert gas atmosphere and sealed. The assembled plurality of battery bodies 110 are connected in series and then mounted in a battery container, and the positive electrode region 116 of each battery body 110 is communicated with the chlorine gas circulation device 120. The negative electrode region 117 of each cell body 110 is communicated with the electrolyte circulation means 130.
The chlorine lithium battery 100 is used in combination with a solar power generation apparatus and a wind power generation apparatus and supplies power to a load circuit.
Comparative example
The specific energy was calculated by taking the lithium chloride battery 100 of example 3 as an example.
The general reaction formula of the lithium chloride battery 100: li +1/2Cl2＝1/2LiCl
6.941 35.5
Average voltage of the chlorine lithium battery 100: ev 1.36- (-3.042) ═ 4.402V
Energy of 1mol Li production: 4.402V × 96485C-424726.97J-117.98 Wh
Energy production by 1kg Li (1kg Li consumes about 5.11kg Cl2)：
(1000/6.941)×117.98/1000＝16.998KWh
From this, it is found that the specific energy is 16.998KWh/(1Kg +5.11Kg) and 2.782 KWh/Kg. Therefore, the lithium chloride battery 100 has a high specific energy.
The energy storage density, charging time, efficiency, lifetime, and power density of the lithium chloride batteries 100 prepared in examples 1 to 4 were calculated and compared with the existing various energy storage methods, and the results are shown in table 1.
TABLE 1 comparison of parameters of lithium chloride batteries with existing energy storage methods
As can be seen from the above table, the present lithium chloride battery 100 has a greater energy storage density, a higher efficiency, a lifetime that tends to be unlimited, and a better power density. Since the lithium chloride battery 100 has the above advantages, the lithium chloride battery 100 has: the power fluctuation of the renewable energy power generation is stabilized, the electric energy quality is improved, and the peak load regulation pressure of a power grid is relieved; the capacity requirement of the matched power transmission line can be reduced, and the utilization rate of the existing power transmission, transmission and distribution equipment is improved; the stability of the power system is enhanced; reducing rotation for standby; the power generation coal consumption and the power supply loss are reduced, and the power consumption cost of a user is reduced; the power supply reliability is improved, and the power failure loss is reduced.
In summary, it can be seen from the embodiments 1 to 4 that the lithium chloride battery 100 not only has the characteristics of large capacity, high efficiency, large density, etc., but also has the characteristic of long service life. Therefore, the chlorine lithium battery 100 is used in cooperation with the intermittent power generation device, stable energy storage of the large-scale intermittent power generation device can be realized, the economy, safety and reliability of a power grid can be improved, the new energy utilization and development which is vigorously advocated by the nation at present are met, and the chlorine lithium battery has remarkable economic and social benefits.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (6)
1. A chlorine lithium battery is characterized by comprising a battery body, a chlorine circulating device and an electrolyte circulating device, wherein the chlorine circulating device is used for storing chlorine, the electrolyte circulating device is used for storing electrolyte, the battery body comprises a shell and a membrane assembly, the membrane assembly is arranged in the shell and divides the shell into a positive electrode area and a negative electrode area, lithium salt non-aqueous electrolyte is arranged in the shell, a positive electrode plate for chlorine reaction is arranged in the positive electrode area, a negative electrode plate is arranged in the negative electrode area, the positive electrode area is communicated with the chlorine circulating device, and the negative electrode area is communicated with the electrolyte circulating device;
the chlorine circulating device comprises a chlorine circulating tank and a chlorine source, the anode area is communicated with the chlorine circulating tank, and the chlorine source is communicated with the circulating tank;
the pipeline communicated between the chlorine gas circulating tank and the anode region comprises a first pipeline for inputting chlorine gas into the anode region and a second pipeline for removing the chlorine gas from the anode region, and the first pipeline and the second pipeline are respectively provided with a regulating valve for balancing pressure;
two ends of the first pipeline are respectively communicated with the chlorine gas circulating tank and the shell positioned at the bottom of the anode region, and two ends of the second pipeline are respectively communicated with the chlorine gas circulating tank and the shell positioned at the upper part of the anode region;
the chlorine circulating tank is communicated with the chlorine circulating tank, and a pipeline communicated between the absorption mechanism and the chlorine circulating tank is provided with a regulating valve;
the electrolyte circulating device comprises an electrolyte circulating tank and a circulating pump, the electrolyte circulating tank is communicated with the pipeline of the negative electrode area, the pipeline of the negative electrode area comprises a third pipeline for inputting the electrolyte into the shell and a fourth pipeline for discharging the electrolyte out of the shell, the third pipeline is provided with the circulating pump and a fourth regulating valve, and the fourth pipeline is provided with a fifth regulating valve.
2. The chlorine lithium battery as claimed in claim 1, wherein said positive plate is selected from graphite or platinum.
3. The chlorine lithium battery as claimed in claim 1, wherein the electrolyte comprises a lithium salt and an organic solvent, and the organic solvent is at least one selected from the group consisting of carbonate compounds, carboxylic acid compounds, ether compounds and nitrile compounds.
4. The chlorine lithium battery as claimed in claim 3, wherein the carbonate-based compound is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; the carboxylic acid compound is at least one selected from melamine formaldehyde resin, methyl acrylate, ethyl acrylate and gamma-butyrolactone; the ether compound is at least one of tetrahydrofuran, 2-methyl-tetrahydrofuran and dimethoxymethane; the nitrile compound is selected from the group consisting of fluorodinitriles.
5. The chlorine lithium battery of claim 3, wherein said lithium salt is selected from LiCl or from LiCl and LiClO4、LiPF6、LiBF4、LiAsF6、Li(CF3CO2)2N、LiCF3SO3、Li(CF3SO2)3、Li(CF3SO2)2N、Li(C2F5SO2)2N、LiB(C2O4)2A mixture of at least one of the above.
6. An energy storage method using a chlorine lithium battery as claimed in any one of claims 1 to 5, characterized in that a power generation device is electrically connected to the chlorine lithium battery, an electrolyte is fed into the chlorine lithium battery, and the generated chlorine gas is collected for recycling.
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| CN107528051A (en) * | 2017-08-09 | 2017-12-29 | 徐州工程学院 | A kind of lithium chlorine one-shot battery |
| CN108321434A (en) * | 2018-03-23 | 2018-07-24 | 安普瑞斯（无锡）有限公司 | A kind of high-voltage lithium-ion battery electrolyte |
| CN115939450B (en) * | 2022-12-20 | 2024-04-12 | 河南科技大学 | Aluminum-potassium ferrocyanide energy-saving battery circulation device |
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| US4020238A (en) * | 1973-07-02 | 1977-04-26 | Energy Development Associates | Control of generation of chlorine feed from chlorine hydrate for use in a metal chlorine electric energy storage device |
| US4049880A (en) * | 1976-06-11 | 1977-09-20 | Energy Development Associates | Self-generating halogen liquification in a secondary battery |
| JPS57119469A (en) * | 1981-01-17 | 1982-07-24 | Furukawa Battery Co Ltd:The | Zinc-halogen battery system |
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