CN107968230B - Liquid metal battery - Google Patents
Liquid metal battery Download PDFInfo
- Publication number
- CN107968230B CN107968230B CN201711097608.0A CN201711097608A CN107968230B CN 107968230 B CN107968230 B CN 107968230B CN 201711097608 A CN201711097608 A CN 201711097608A CN 107968230 B CN107968230 B CN 107968230B
- Authority
- CN
- China
- Prior art keywords
- metal battery
- insulating
- positive
- lead
- crucible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 109
- 239000002184 metal Substances 0.000 claims abstract description 109
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000007774 positive electrode material Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000007773 negative electrode material Substances 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000007789 sealing Methods 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011257 shell material Substances 0.000 description 57
- 239000000919 ceramic Substances 0.000 description 14
- 239000007769 metal material Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 101100298225 Caenorhabditis elegans pot-2 gene Proteins 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004553 extrusion of metal Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/399—Cells with molten salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
The invention relates to the technical field of liquid metal batteries, in particular to a liquid metal battery which can effectively lead out a positive electrode, improve the reliability of a sealing effect, avoid leakage of positive and negative electrode materials and electrolytic salt, and improve the service life and safety performance of the battery. The present invention provides a liquid metal battery comprising: the battery comprises a metal battery shell and an insulating crucible arranged inside the metal battery shell, wherein the insulating crucible is of a cylindrical structure with a closed lower end and an open upper end, and a positive electrode material, an electrolyte and a negative electrode material are sequentially arranged in the insulating crucible from bottom to top; the positive electrode material is electrically connected with the metal battery shell through a positive electrode lead wire; at least one part of the positive lead wire is immersed in the positive material and is electrically connected with the positive material, and is led out through the upper end opening of the insulating crucible and is electrically connected with the metal battery shell, and the outer side of the part of the positive lead wire, corresponding to the electrolyte and the negative material, is provided with an insulating protection device.
Description
Technical Field
The invention relates to the technical field of liquid metal batteries, in particular to a liquid metal battery.
Background
A liquid metal battery is a high temperature battery, and in operation, all parts of the liquid metal battery exist in liquid form: a low-density liquid metal cathode, a molten salt electrolyte, and a high-density liquid metal anode. The three parts are naturally divided into three layers because of different densities and mutual insolubility. During discharge, the negative metal loses electrons and works through an external circuit. After ionization, the metal of the negative electrode is transferred to the positive electrode through molten salt and is alloyed with the metal of the positive electrode. When charging, the battery performs the reverse process. Through the alloying and dealloying processes, the liquid metal battery can complete the storage and release of electric energy, and realize the energy exchange with the outside.
The chemical properties of positive and negative electrode materials and molten salt in the liquid metal battery are very active, and the liquid metal battery is very easy to react with water and oxygen in the air to cause the battery to lose efficacy, so that the integral sealing of the liquid metal battery under the conditions of normal temperature and high temperature is a very important safety problem.
In the prior art, in order to seal a liquid metal battery, a metal battery case is generally used to encapsulate positive and negative electrode materials and electrolytic salt, however, when the liquid metal battery operates at a high temperature, insulation isolation is maintained between the positive and negative electrodes, and charging and discharging can be performed according to a specified path if the liquid metal battery allows the positive and negative electrodes to be in short circuit, in order to prevent the short circuit of the positive and negative electrodes inside the battery, a way of coating an insulating ceramic layer on the inner wall of the metal battery case is generally adopted, or a way of installing an insulating ceramic tube inside the metal battery case is adopted, as shown in fig. 1, the insulating ceramic tube 2 and the bottom of the metal battery case 1 are sealed by using a high-temperature sealant, so as to encapsulate the positive and negative electrode materials and the electrolytic salt inside the insulating ceramic tube 2, and at the same time, insulation between the positive.
However, when the insulating ceramic layer is coated on the inner wall of the metal battery shell to prevent the short circuit of the positive electrode and the negative electrode, the processing technology is complex, the cost is high, and the insulating ceramic layer and the metal battery shell have different thermal expansion coefficients, so that the insulating ceramic layer is easy to crack and fall off in a high-temperature operation environment; when the insulating ceramic tube is arranged in the metal battery shell to prevent the short circuit of the positive electrode and the negative electrode, the bottom of the insulating ceramic tube and the bottom of the metal battery shell need to be coated with high-temperature-resistant insulating sealant, if the local position is cracked, leakage of positive and negative electrode materials and electrolytic salt is easy to occur, so that the performance of the battery is reduced or even loses efficacy, and the leakage of the positive and negative electrode materials and molten electrolytic salt is easy to occur along with the corrosion of the molten positive and negative electrode materials and electrolytic salt to the metal battery shell, so that fire and explosion are easy to cause.
Disclosure of Invention
The embodiment of the invention provides a liquid metal battery, which can effectively lead out a positive electrode, improve the reliability of a sealing effect, avoid leakage of positive and negative electrode materials and electrolytic salt, and improve the service life and safety performance of the battery.
To achieve the above object, an embodiment of the present invention provides a liquid metal battery including:
the battery comprises a metal battery shell and an insulating crucible arranged inside the metal battery shell, wherein the insulating crucible is of a cylindrical structure with a closed lower end and an open upper end, and a positive electrode material, an electrolyte and a negative electrode material are sequentially arranged in the insulating crucible from bottom to top;
the positive electrode material is electrically connected with the metal battery shell through a positive electrode lead wire;
at least one part of the positive lead wire is immersed in the positive material and is electrically connected with the positive material, and is led out through the upper end opening of the insulating crucible and is electrically connected with the metal battery shell, and the outer side of the part of the positive lead wire, corresponding to the electrolyte and the negative material, is provided with an insulating protection device.
Optionally, the insulation protection device includes: a lead laying hole for leading out the anode lead wire is arranged in the side wall of the insulating crucible and extends along the height direction of the side wall; or an insulating tube which is arranged on the inner side of the side wall of the insulating crucible and is used for leading out the anode lead-out wire, and the insulating tube is fixedly connected with the inner side wall of the insulating crucible.
Optionally, two ends of the wire laying hole are respectively connected with the positive electrode outgoing wire in a sealing manner.
Optionally, the insulating tube is vertically arranged, an upper end opening of the insulating tube is provided, a lead leading-out hole communicated with the anode material is formed in the lower end of the insulating tube, and the anode leading-out wire penetrates through the lead leading-out hole and is led out through the upper end opening of the insulating tube and electrically connected with the metal battery shell.
Optionally, the lead wire leading-out hole and the upper end opening of the insulating tube are respectively connected with the positive electrode leading-out wire in a sealing manner.
Optionally, the number of the positive electrode lead-out wires is one or more than two.
Optionally, the middle part of the positive electrode lead-out wire is immersed in the positive electrode material and electrically connected with the positive electrode material, two ends of the positive electrode lead-out wire are respectively led out through an upper end opening of the insulating crucible and electrically connected with the metal battery shell, and two ends of the positive electrode lead-out wire are symmetrically distributed along two sides of the central axis of the insulating crucible.
Optionally, when the number of the positive lead wires is more than two, one end of each positive lead wire is immersed in the positive material and electrically connected with the positive material, the other end of each positive lead wire is led out through an opening at the upper end of the insulating crucible and electrically connected with the metal battery shell, and the positive lead wires are uniformly distributed along the circumferential direction of the central axis of the insulating crucible.
Optionally, a gap which is more than or equal to 10% of the thickness of the insulating crucible and less than or equal to 80% of the thickness of the insulating crucible is reserved between the side wall of the insulating crucible and the side wall of the metal battery shell; a gap of 3-10mm is reserved between the upper end of the insulating crucible and the top surface of the metal battery shell; a gap of 0.3-2mm is left between the lower end of the insulating crucible and the bottom surface of the metal battery shell.
Optionally, the metal battery shell comprises an upper half shell and a lower half shell, wherein the insulating crucible is located in the lower half shell, the upper half shell is connected with a cathode rod in a sealing mode, one end of the cathode rod extends into the cathode material and is connected with the lower half shell in a sealing mode, and the other end of the cathode rod is located outside the upper half shell.
The embodiment of the invention provides a liquid metal battery, which can ensure the sealing performance of positive and negative electrode materials and electrolyte by replacing a ceramic tube with an insulating crucible, prevent the leakage of the positive and negative electrode materials and the electrolyte because the lower end of the insulating crucible is closed, simultaneously realize the electric connection of the positive electrode materials and a metal battery shell by additionally arranging a positive lead wire, realize the normal export of a positive electrode by arranging an insulating protection device at the outer side of the part of the positive lead wire corresponding to the electrolyte and a negative electrode material, improve the reliability of the sealing effect while effectively exporting the positive electrode and avoid the leakage of the positive and negative electrode materials and the electrolyte salt compared with the prior art that the lower end of the ceramic tube is hermetically connected with the bottom surface of the metal battery shell to realize the seal of the positive electrode materials and the electrolyte salt and directly connect the positive electrode materials with the metal battery shell to realize the export of the positive electrode, the service life and the safety performance of the battery are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a liquid metal battery provided in the prior art;
fig. 2 is a schematic structural diagram of a liquid metal battery according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of another liquid metal battery according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of another liquid metal battery according to an embodiment of the present invention;
fig. 5 is a schematic structural diagram of another liquid metal battery according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, and do not indicate or imply that the referenced device or assembly must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
An embodiment of the present invention provides a liquid metal battery, referring to fig. 2 and 3, including:
the battery comprises a metal battery shell 1 and an insulating crucible 2 arranged inside the metal battery shell 1, wherein the insulating crucible 2 is of a cylindrical structure with a closed lower end and an open upper end, and a positive electrode material, an electrolyte and a negative electrode material are sequentially arranged in the insulating crucible 2 from bottom to top;
the positive electrode material is electrically connected with the metal battery shell 1 through a positive electrode lead-out wire 3;
at least one part of the positive lead wire 3 is immersed in the positive material and is electrically connected with the positive material, and is led out through the upper end opening of the insulating crucible 2 and is electrically connected with the metal battery shell, and the outer side of the part of the positive lead wire 3 corresponding to the electrolyte and the negative material is provided with an insulating protection device 4.
Wherein, the insulating crucible is a structure similar to a clay pot made of insulating materials.
The portion of the positive electrode lead wire 3 corresponding to the electrolyte and the negative electrode material means a portion of the positive electrode lead wire 3 directly contacting the electrolyte and the negative electrode material when the insulating protection device 4 is not provided.
It should be noted that, because the negative electrode material of the battery is generally a simple substance or an alloy of an alkali metal or an alkaline earth metal, the positive electrode material is generally a transition metal simple substance, an alloy or other compounds which can form an alloy with the negative electrode material and have a certain potential difference with the negative electrode material. The electrolyte is an inorganic salt or a mixture thereof corresponding to the negative electrode material. Particularly, when the lithium ion battery is operated at high temperature, the positive electrode material, the negative electrode material and the electrolytic salt have strong activity, and are easy to generate chemical reaction with the metal material to cause corrosion of the metal material, and because the positive lead-out wire 3 is usually made of the metal material, and the positive lead-out wire 3 is in short circuit when being directly contacted with the negative electrode material, the insulating protection device 4 is arranged on the outer side of the part of the positive lead-out wire 3 corresponding to the electrolyte and the negative electrode material, so that the corrosion of the positive lead-out wire 3 by the electrolyte can be prevented, and meanwhile, the normal leading-out of the positive electrode can be ensured.
The embodiment of the invention provides a liquid metal battery, which can ensure the sealing performance of positive and negative electrode materials and electrolyte by replacing a ceramic tube with an insulating crucible 2, prevent the leakage of the positive and negative electrode materials and the electrolyte because the lower end of the insulating crucible 2 is closed, realize the electric connection of the positive electrode material and a metal battery shell 1 by additionally arranging a positive lead wire 3, realize the normal export of a positive electrode by arranging an insulating protection device 4 at the outer side of the part of the positive lead wire 3 corresponding to the electrolyte and a negative electrode material, realize the sealing of the positive and negative electrode materials and electrolytic salt by hermetically connecting the lower end of the ceramic tube with the bottom surface of the metal battery shell 1 in the prior art, improve the reliability of the sealing effect while effectively exporting the positive electrode, the leakage of positive and negative electrode materials and electrolytic salt is avoided, and the service life and the safety performance of the battery are improved.
Wherein, the insulating crucible 2 can be made of any insulating material, such as ceramic material and the like.
Further, in the embodiment of the invention, the insulating crucible 2 is not in direct contact with the metal battery shell 1, so that a wider choice is brought to the manufacturing material of the metal battery shell 1, any metal can be selected as the battery shell material, the material of the metal battery shell 1 is not limited in the material range of low expansion coefficient, and the battery cost can be reduced.
The method of connecting the positive electrode lead wire 3 to the metal battery case 1 is not limited.
In practical applications, since the metal battery case 1 is generally made of stainless steel or mild steel, it is preferable that the positive electrode lead wire 3 be electrically connected to the metal battery case 1 by welding or riveting.
The arrangement mode of the positive lead wire 3 in the insulating crucible 2 is not limited, one end of the positive lead wire 3 can be immersed in the positive material to be electrically connected with the positive material, and the other end of the positive lead wire 3 is led out through an upper end opening of the insulating crucible to be electrically connected with the metal battery shell 1. The length of the positive electrode lead-out wire 3 provided in the positive electrode material is not limited as long as the positive electrode material and the metal battery case 1 can be electrically connected to each other through the positive electrode lead-out wire 3.
The number of the positive electrode lead wires 3 is not limited, and the positive electrode material and the metal battery case 1 may be electrically connected by one positive electrode lead wire 3, or the positive electrode material and the metal battery case 1 may be electrically connected by a plurality of positive electrode lead wires 3.
In an embodiment of the present invention, the number of the positive electrode lead wires 3 is one or more than two.
Wherein, do not do the restriction to the setting mode of anodal lead-out wire 3, when anodal lead-out wire is one or more than two, a setting mode does, see figure 4, and the middle part submergence of anodal lead-out wire 3 is connected with the anodal material electricity in the anodal material, and the both ends of anodal lead-out wire 3 are drawn forth through the upper end opening of insulating crucible 2 respectively and are connected with metal battery shell 1 electricity, and the bilateral symmetry of the central axis along insulating crucible 2 distributes at the both ends of anodal lead-out wire 3. Through the middle part submergence with anodal lead-out wire 3 in anodal material, both ends are connected with the 1 electricity of metal battery shell with the form of symmetry, on the one hand, can increase the tie point between anodal lead-out wire 3 and the metal battery shell 1, and on the other hand can also make the atress of insulating crucible 2 in metal battery shell 1 comparatively balanced to can improve the steadiness of insulating crucible 2, prevent that insulating crucible 2 from taking place to rock.
When the number of the positive lead wires 3 is more than two, another possible arrangement is that, referring to fig. 5, one end of each positive lead wire 3 is immersed in the positive material and electrically connected with the positive material, the other end of each positive lead wire is led out through the upper end opening of the insulating crucible 2 and electrically connected with the metal battery shell 1, and the positive lead wires 3 are uniformly distributed along the circumferential direction of the central axis of the insulating crucible 2. Adopt this kind of mode of setting up, can increase the tie point between anodal lead-out wire 3 and the metal battery casing 1 equally for the atress of insulating crucible 2 in metal battery casing 1 is comparatively balanced, thereby can improve insulating crucible 2's steadiness, prevents that insulating crucible 2 from taking place to rock.
Meanwhile, by adopting the two setting modes, the contact area between the anode leading-out wire 3 and the anode material can be increased, and the conductive effect is improved.
In an embodiment of the present invention, referring to fig. 3 and 4, the insulation protection device 4 includes: a lead laying hole 5 which is arranged inside the side wall 21 of the insulating crucible 2 and extends along the height direction of the side wall 21 and is used for leading out the positive lead wire 3; or an insulating tube 6 which is arranged on the inner side of the side wall 21 of the insulating crucible 2 and is used for leading out the anode leading-out wire 3, and the insulating tube 6 is fixedly connected with the inner side wall of the insulating crucible 2.
In the embodiment of the invention, by adopting the two modes, the insulation of the part of the positive lead wire 3 corresponding to the electrolyte and the negative electrode material can be realized, and the phenomena that the positive lead wire 3 is exposed in the electrolytic salt to be corroded and the positive lead wire 3 is exposed in the negative electrode material to generate short circuit so that the positive electrode cannot be led out normally are prevented.
When the positive lead wire 3 is one, a wire laying hole 5 can be formed in the side wall of the insulating crucible 2, one end of the positive lead wire 3 is immersed in the positive material, and the other end of the positive lead wire is led out through the wire laying hole 5 to be electrically connected with the metal battery shell 1; or two lead laying holes 5 can be arranged on the side wall of the insulating crucible 2, the middle part of the anode leading-out wire 3 is immersed in the anode material, and the two ends are respectively led out through the two lead laying holes 5, and are respectively electrically connected with the metal battery shell 1, the two lead laying holes 5 can be symmetrically arranged along the two sides of the central axis of the insulating crucible 2, the stability of the connection between the anode leading-out wire 3 and the metal battery shell 1 can be improved, further, the stress of the insulating crucible 2 in the metal battery shell 1 is relatively balanced, two insulating pipes 6 can be arranged in the insulating crucible 2, the middle part of the anode lead-out wire 3 is immersed in the anode material, the two ends are respectively led out through the two insulating tubes 6, and are respectively electrically connected with the metal battery shell 1, the two insulating tubes 6 can be symmetrically distributed along two sides of the central axis of the insulating crucible 2, and the stress of the insulating crucible 2 in the metal battery shell 1 can be balanced. An insulating tube 6 can be arranged on one side of the insulating crucible 2, a wire laying hole 5 is formed in the side wall 21 on the other side, the middle of the positive electrode lead-out wire 3 is immersed in the positive electrode material, one end of the positive electrode lead-out wire is led out through the insulating tube 6 to be electrically connected with the metal battery shell 1, and the other end of the positive electrode lead-out wire is led out through the wire laying hole 5 to be electrically connected with the metal battery shell 1.
And when anodal lead-out wire 3 is more than two, can set up a plurality of wires correspondingly and lay hole 5 on insulating crucible 2's lateral wall, wear to locate a plurality of wires respectively with these anodal lead-out wires 3 and lay in hole 5, and lay the tip of these anodal lead-out wires 3 through the wire respectively and lay hole 5 and draw out and be connected with metal battery shell 1 electricity, these wires lay hole 5 and can follow the circumference of insulating crucible 2's the central axis and evenly arrange, can improve the steadiness that anodal lead-out wire 3 and metal battery shell 1 are connected, and then can make insulating crucible 2 atress comparatively balanced in metal battery shell 1. Also can set up insulating tube 6 more than two in insulating crucible 2, wear to locate in insulating tube 6 respectively with these anodal lead-out wires 3 to draw forth the tip of these anodal lead-out wires 3 respectively through the upper end opening of insulating tube 6 and be connected with metal battery casing 1 electricity, insulating tube 6 more than these two also can be along the circumference evenly distributed of insulating crucible 2's the central axis, can make insulating crucible 2 comparatively balanced in the stress of metal battery casing 1 equally. Of course, can also both set up the wire in insulating crucible 2's lateral wall and lay hole 5, set up insulating tube 6 in it again to wear to locate wire and lay hole 5 and insulating tube 6 with anodal lead-out wire 3 respectively, can be with anodal lead-out wire along insulating crucible 2's the circumference evenly distributed of the central axis, can reach the comparatively balanced purpose of messenger insulating crucible 2 atress in metal battery shell 1 equally.
In order to prevent the positive and negative electrode materials from entering the lead-wire application hole 5, it is preferable that both ends of the lead-wire application hole 5 are hermetically connected to the positive lead-out wire 3, respectively.
The arrangement mode of the insulating tube 6 is not limited, and the insulating tube 6 can be obliquely arranged or vertically arranged.
Illustratively, the insulating tube 6 is vertically arranged, an upper end of the insulating tube 6 is open, a lead wire leading-out hole 61 communicated with the anode material is formed at a lower end of the insulating tube 6, and the anode leading-out wire 3 is inserted into the insulating tube 6 through the lead wire leading-out hole 61, led out through the upper end opening of the insulating tube 6 and electrically connected with the metal battery shell 1.
In order to prevent the positive and negative electrode materials from being impregnated into the insulating tube 6 during the operation of the battery, it is preferable that the lead wire drawing hole 61 and the upper end opening of the insulating tube 6 are hermetically connected to the positive electrode drawing wire 3, respectively.
Wherein the fixed connection mode between the insulating pipe 6 and the inner side wall of the insulating crucible 2 is not limited.
Because the inside of the insulating crucible 2 is in a high-temperature operation environment, preferably, the insulating tube 6 is fixedly connected with the inner side wall of the insulating crucible 2 through high-temperature sealant. Therefore, the high-temperature insulating device can adapt to a high-temperature operation environment, and avoids cracking between the insulating pipe 6 and the insulating crucible 2.
In still another embodiment of the present invention, the positive electrode lead-out wire 3 is extended in a curved line. The extension arrangement in a curve form means that a certain amount of extension and contraction is reserved between the end, connected with the positive electrode material, of the positive electrode lead-out wire 3 and the end, connected with the metal battery shell 1, of the positive electrode lead-out wire, and flexible connection between the insulating crucible 2 and the metal battery shell 1 can be achieved.
Preferably, the positive electrode lead wire 3 has a thermal expansion coefficient of 6 × 10-6/℃-10×10-6A metallic material at/° c. The object has a swelling and shrinking phenomenon due to temperature change. The change capability is expressed by the volume change, namely the thermal expansion coefficient, caused by unit temperature change under the condition of equal pressure (P is constant), in practical application, because the anode outgoing line 3 is arranged in a high-temperature area and is in direct contact with an anode material and is arranged on the side wall of the insulating crucible 2 in a penetrating way or arranged on the insulating tube 6 in a penetrating way, the metal material with the thermal expansion coefficient close to the insulating material is selected as the anode outgoing line 3, and the phenomenon that the insulating crucible 2 or the insulating tube 6 cracks due to the fact that the thermal expansion coefficient between the anode outgoing line 3 and the insulating crucible 2 or the insulating tube 6 is large under high temperature can be avoided. All in oneDuring the time, when the both ends of wire laying hole 5 and anodal lead-out wire 3 sealing connection, perhaps, when the wire draws out hole 61 and the upper end opening part of insulating tube 6 respectively with anodal lead-out wire 3 sealing connection, adopt high temperature sealed glue to carry out sealing connection usually, at this moment, adopt these materials as anodal lead-out wire 3, can also prevent to cause the sealed cracking of glue of high temperature because of the difference of thermal expansion coefficient under the high temperature, improve sealed effect.
The metal material has different thermal expansion coefficients due to different manufacturing processes and compositions, for example, stainless steel, some of which have a larger thermal expansion coefficient and some of which have a smaller thermal expansion coefficient, so the positive lead wire 3 may be selected from any one of stainless steel, tungsten, molybdenum, tantalum, nickel, and titanium, which have a smaller thermal expansion coefficient. The positive lead-out wire 3 made of the materials has the advantages of high temperature resistance, strong corrosion resistance and good conductivity, and can improve the conductivity of the battery.
Further, compared with the prior art in which the metal battery case is directly led out as the positive electrode, the embodiment of the invention can lead out the positive electrode by using a very small amount of these materials as the positive electrode lead-out wire 3, and does not need to replace the whole metal battery case with these materials, so that the conductivity of the battery can be greatly improved at the cost-saving condition.
In an embodiment of the invention, with continued reference to fig. 2, 3, 4 and 5, a gap d2 remains between the side wall 21 of the insulating crucible 2 and the side wall 13 of the metal battery case 1 that is greater than or equal to 10% of the thickness d1 of the insulating crucible 2 and less than or equal to 80% of the thickness d1 of the insulating crucible 2. Because insulating crucible 2 is located the high temperature region, consequently, through leaving clearance d2 between insulating crucible 2 and metal battery case 1, can avoid insulating crucible 2 and the expansion of metal battery case 1 and produce the extrusion under high temperature, cause breaking of insulating crucible 2.
Since the positive electrode lead-out wire 3 is led out through the upper end opening of the insulating pot 2 to be electrically connected to the metal battery case 1, it is preferable that, with continued reference to fig. 2, 3, 4 and 5, a gap d3 of 3 to 10mm is left between the upper end of the insulating pot 2 and the top surface of the metal battery case 1. Wherein, the upper end of insulating crucible 2 is the border position that the peak of insulating crucible 2 corresponds, and the top surface of metal battery casing 1 is the medial surface at the top of metal battery casing 1 then, so, make things convenient for going on of anodal lead-out wire 3 and metal battery casing 1 connection operation.
Illustratively, the positive electrode lead-out wire 3 may be electrically connected to the metal battery case 1 by welding or riveting. The welding or riveting between the positive electrode lead-out wire 3 and the metal battery shell 1 can be conveniently carried out.
In still another preferred embodiment of the present invention, with continued reference to fig. 2, 3, 4 and 5, a gap d4 of 0.3-2mm is left between the lower end of the insulating crucible 2 and the bottom surface of the metal battery case 1. The lower extreme of insulating crucible 2 is the border position that the minimum of insulating crucible corresponds, and the bottom surface of metal battery casing 1 is the bottom medial surface of metal battery casing 1, reserves certain space through the bottom at metal battery casing 1, can reserve certain expansion space for insulating crucible 2, avoids extruding between insulating crucible 2 and the metal battery casing 1 and takes place to break.
Further, through reserving a certain space, can also fill thermal-insulated cotton in the clearance between insulating crucible 2 and the metal battery casing 1 (the clearance here includes clearance d2 between lateral wall 21 of insulating crucible 2 and the lateral wall 13 of metal battery casing 1, clearance d3 between the upper end of insulating crucible 2 and the top surface of metal battery casing 1, and clearance d4 between the lower extreme of insulating crucible 2 and the bottom surface of metal battery casing 1), can avoid insulating crucible 2 to take place to rock while, keep warm to the high temperature environment, and simultaneously, because thermal-insulated cotton is flexible material, can cushion insulating crucible 2's thermal energy, avoid insulating crucible 2 and the direct rigid extrusion of metal battery casing 1 to take place to break.
In practical applications, after the positive lead wire 3 is welded or riveted with the metal battery case 1, a through hole may be formed in the metal battery case 1 to lead out the positive lead wire 3, so as to be electrically connected to an external circuit.
Further, the positive electrode lead wire 3 may be hermetically connected to a through hole formed in the metal battery case 1 through the lead-out positive electrode lead wire 3. The high temperature environment in which the battery operates can be maintained.
In an embodiment of the present invention, with continued reference to fig. 2, fig. 3, fig. 4, and fig. 5, the metal battery case 1 includes an upper half case 11 and a lower half case 12, wherein the insulating pot 2 is located in the lower half case 12, the upper half case 11 is hermetically connected to the negative electrode rod 7, and is hermetically connected to the lower half case 12 by extending one end of the negative electrode rod 7 into the negative electrode material, and the other end of the negative electrode rod 7 is located outside the upper half case 11.
In the embodiment of the invention, the metal battery case 1 is composed of two parts, when assembling the battery, the opening of the insulating crucible 2 provided with the lead laying hole 5 is placed upwards in the lower half case 12, the positive lead wire 3 is inserted into the lead laying hole 5, one end is electrically connected with the positive material, the other end is electrically connected with the lower half case 12, or the opening of the insulating crucible 2 not provided with the lead laying hole 5 is placed upwards in the lower half case 12, the insulating tube 6 with openings at two ends is vertically arranged and fixedly connected with the inner side wall of the insulating crucible 2 through the high temperature sealant, the positive lead wire 3 is inserted into the insulating tube 6 and electrically connected with the positive material and the lower half case 12, then the positive material, the electrolytic salt and the negative material are sequentially added into the insulating crucible 2, and the upper half case 11 hermetically connected with the negative rod 4 is hermetically connected with the upper half case 12, so that one end of the negative electrode rod 4 protrudes into the negative electrode material and the other end is located outside the upper half casing 11. And the sealing and the assembly of the battery are facilitated.
In a preferred embodiment of the present invention, the upper housing half 11 and the lower housing half 12 are sealingly connected. For example, the bolts 8 can be used for fixing by using a method of sealing metal flanges in vacuum equipment by virtue of the sealing connection of the bolts 8 and the sealing gaskets, and compared with a welding mode, the bolts 8 can be detached at any time, so that the battery can be replaced and maintained.
The connection mode of the upper half casing 11 and the negative electrode rod 7 is not limited, and since the upper half casing 11 is usually made of a metal material, the upper half casing 11 and the negative electrode rod 7 can be hermetically connected in a brazing mode, and specifically, the negative electrode rod 7 can penetrate through the middle of the upper half casing 11.
In order to further improve the insulation effect, it is preferable that a negative insulating ceramic 9 is further provided between the upper half casing 11 and the negative electrode rod 7.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A liquid metal battery, comprising:
the battery comprises a metal battery shell and an insulating crucible arranged inside the metal battery shell, wherein the insulating crucible is of a cylindrical structure with a closed lower end and an open upper end, and a positive electrode material, an electrolyte and a negative electrode material are sequentially arranged in the insulating crucible from bottom to top;
the positive electrode material is electrically connected with the metal battery shell through a positive electrode lead wire;
at least one part of the positive lead wire is immersed in the positive material and is electrically connected with the positive material, and is led out through an upper end opening of the insulating crucible and is electrically connected with the metal battery shell, and an insulating protection device is arranged on the outer side of the part, corresponding to the electrolyte and the negative material, of the positive lead wire;
the insulation protection device includes: the lead laying hole is arranged in the side wall of the insulating crucible and extends along the height direction of the side wall, and the lead laying hole is used for leading out the positive lead wire; or the insulating tube is arranged on the inner side of the side wall of the insulating crucible and used for leading out the anode lead-out wire, and the insulating tube is fixedly connected with the inner side wall of the insulating crucible.
2. The liquid metal battery of claim 1,
and two ends of the wire laying hole are respectively connected with the positive electrode lead-out wire in a sealing manner.
3. The liquid metal battery of claim 1,
the insulating tube is vertically arranged, the upper end of the insulating tube is provided with an opening, the lower end of the insulating tube is provided with a lead leading-out hole communicated with the anode material, and the anode leading-out wire penetrates through the insulating tube through the lead leading-out hole, is led out through the upper end opening of the insulating tube and is electrically connected with the metal battery shell.
4. The liquid metal battery of claim 3,
the lead leading-out hole and the upper end opening of the insulating tube are respectively connected with the anode leading-out wire in a sealing mode.
5. The liquid metal battery of claim 1,
the positive lead wire is one or more than two.
6. The liquid metal battery of claim 5,
the middle part of the positive electrode lead-out wire is immersed in the positive electrode material and is electrically connected with the positive electrode material, two ends of the positive electrode lead-out wire are respectively led out through an upper end opening of the insulating crucible and are electrically connected with the metal battery shell, and two ends of the positive electrode lead-out wire are symmetrically distributed along two sides of the central axis of the insulating crucible.
7. The liquid metal battery of claim 5,
when the number of the positive lead wires is more than two, one end of each positive lead wire is immersed in the positive material and is electrically connected with the positive material, the other end of each positive lead wire is led out from an upper end opening of the insulating crucible and is electrically connected with the metal battery shell, and the positive lead wires are uniformly distributed along the circumferential direction of the central axis of the insulating crucible.
8. The liquid metal battery of claim 1,
a gap which is more than or equal to 10% of the thickness of the insulating crucible and less than or equal to 80% of the thickness of the insulating crucible is reserved between the side wall of the insulating crucible and the side wall of the metal battery shell; a gap of 3-10mm is reserved between the upper end of the insulating crucible and the top surface of the metal battery shell; and a gap of 0.3-2mm is reserved between the lower end of the insulating crucible and the bottom surface of the metal battery shell.
9. The liquid metal battery of claim 1,
the metal battery shell comprises an upper half shell and a lower half shell, wherein the insulating crucible is located in the lower half shell, the upper half shell is connected with a negative rod in a sealing mode, one end of the negative rod extends into the negative material, the negative rod is connected with the lower half shell in a sealing mode, and the other end of the negative rod is located outside the upper half shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711097608.0A CN107968230B (en) | 2017-11-09 | 2017-11-09 | Liquid metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711097608.0A CN107968230B (en) | 2017-11-09 | 2017-11-09 | Liquid metal battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107968230A CN107968230A (en) | 2018-04-27 |
| CN107968230B true CN107968230B (en) | 2020-04-21 |
Family
ID=61999954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711097608.0A Active CN107968230B (en) | 2017-11-09 | 2017-11-09 | Liquid metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107968230B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109192889B (en) * | 2018-08-22 | 2024-01-26 | 珠海微矩实业有限公司 | Micro battery |
| CN112331978B (en) * | 2020-11-23 | 2022-04-12 | 中国电子科技集团公司第十八研究所 | High-pressure sealing structure for lead |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010002931A1 (en) * | 2010-03-16 | 2011-09-22 | Helmholtz-Zentrum Dresden - Rossendorf E.V. | Arrangement and method for storing electrical energy in large diameter and high capacity electrochemical cells |
| US10090564B2 (en) * | 2013-03-14 | 2018-10-02 | Massachusettes Institute Of Technology | High amperage batteries with displacement salt electrodes |
| CN204230347U (en) * | 2014-12-12 | 2015-03-25 | 芶富均 | A kind of liquid metal cell device |
| CN105006601A (en) * | 2015-08-12 | 2015-10-28 | 王建平 | Liquid metal battery |
| CN206022520U (en) * | 2016-07-20 | 2017-03-15 | 云南科威液态金属谷研发有限公司 | A kind of room temperature liquid metal battery and consisting of set of cells |
-
2017
- 2017-11-09 CN CN201711097608.0A patent/CN107968230B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107968230A (en) | 2018-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3841912A (en) | Sodium sulfur storage battery | |
| KR102646446B1 (en) | Electrolyte element, and cell containing electrolyte element | |
| CN106654072B (en) | A kind of high-temperature fusant cell apparatus and its preparation process | |
| CN107968230B (en) | Liquid metal battery | |
| CN106972122B (en) | A kind of elevated-temperature seal electrode and preparation method thereof | |
| CN106252543A (en) | Corrosion-resistant sealed insulation device, middle high temperature energy-storage battery and assembly method | |
| US4024320A (en) | Galvanic cells | |
| CN209843832U (en) | Liquid metal battery | |
| US4576881A (en) | Electrochemical storage cell | |
| CN109841910A (en) | A kind of liquid metal cell | |
| CN107946668B (en) | Liquid metal battery | |
| CN104051798B (en) | A kind of sodium-sulphur battery | |
| CN206194804U (en) | Sealed insulation corrosion control system and energy storage battery | |
| CN104562092A (en) | Multi-anode lithium metal electrolytic bath | |
| US20140193698A1 (en) | Electrochemical cell, cell case and method for making same | |
| US20230041604A1 (en) | Electrochemical sodium metal halide battery, and method for producing same | |
| EP0453916A1 (en) | Multilayer cathode current collector/container | |
| CN106159134A (en) | In sealing structure used for high temperature battery, middle high-temperature battery and assembly method thereof | |
| US20140295237A1 (en) | Electrochemical cells useful for energy storage devices | |
| CN206727162U (en) | A kind of multitube sodium-sulphur battery | |
| CN207977356U (en) | A kind of lithium ion battery and its upper cover | |
| US20140168856A1 (en) | Asymmetric electrochemical capacitor positive electrode composition and asymmetric electrochemical capacitor cells and devices comprising same | |
| CN206225485U (en) | A kind of chargeable lithium ion button cell | |
| JP4435925B2 (en) | Sodium battery | |
| US4035553A (en) | Sodium-sulfur electric batteries with ceramic spacer in sulfur compartment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |