CN106469807A - Cathode components, energy accumulating device and method - Google Patents

Cathode components, energy accumulating device and method Download PDF

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Publication number
CN106469807A
CN106469807A CN201510511572.0A CN201510511572A CN106469807A CN 106469807 A CN106469807 A CN 106469807A CN 201510511572 A CN201510511572 A CN 201510511572A CN 106469807 A CN106469807 A CN 106469807A
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metal
oxide
chamber
cathode components
cathode
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CN106469807B (en
Inventor
赵建智
乔布·T·里森比克
王世忠
潘忠文
郭明虎
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General Electric Co
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General Electric Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Abstract

The present invention relates to a kind of cathode components, it includes at least one electroactive metal, the metal-oxide of at least one alkali halide, at least one electrolyte and electrochemicaUy inert, and the metal-oxide of wherein said electrochemicaUy inert does not contain the cation that can carry out ion exchange in electrochemical process and its mean diameter is at 0.01 micron to 100 microns.The invention still further relates to using the energy storing device of described cathode components and the method manufacturing this energy storing device.

Description

Cathode components, energy accumulating device and method
Technical field
This invention relates generally to a kind of electrode material component, more particularly, to a kind of cathode components, Energy storing device and the method preparing described energy storing device using this cathode components.
Background technology
Sodium-metal halide battery, such as sodium-metal chloride battery (sodium metal chloride Batteries) it is considered to be development potentiality very big energy accumulating device because their voltages are high, reason High by specific energy, applied environment is extensive and safe.Sodium-metal halide battery generally comprises melting Metal negative electrode (commonly referred to as anode), the positive pole (for storing or supplying electronics in battery charging and discharging As referred to as negative electrode) and the solid electrolyte as " barrier film " between anode and negative electrode.Sodium-metal halogen It is two main materials that compound battery typically uses sodium halide and electroactive metal such as nickel in the discharged condition Material is in cathode assembling.In charging process, described electroactive metal is in cathode portion by oxygen Change thus forming metal halide, and sodium ion is transferred to anode through electrolyte and is reduced into metal.
Such as, sodium-nickel chloride battery is in the discharged condition as two kinds of chief active materials using sodium chloride and nickel Material, forms in cathode assembling.Described cathode material is immersed in (NaAlCl in sodium terachloroaluminate4), work as operation When 260 DEG C to 340 DEG C, described sodium terachloroaluminate has very strong conductivity to temperature range to sodium ion. In charging process, metallic nickel is oxidized in cathode portion, and sodium ion transfers to anode through electrolyte It is reduced into metal.Basic electrochemical reaction can be by following formula subrepresentation：
Ni+2NaCl→NiCl2+2Na
During electric discharge, sodium is transferred to negative electrode to regenerate sodium halide from anode.In the case of low discharge rate- Mostly it is this situation in stationary applications, existing sodium halide (as sodium chloride) crystal tends to The nucleus of new crystal regrowth.Electrochemistry circulation long-term in such a situa-tion result in cell cathode Halogenation sodium crystal more long bigger.This process is referred to as " roughening " or " ripening ".Halogenation sodium crystal is Just it is smaller in size than 100 microns, size can constantly increase to several millimeters in cyclic process.Crystalline size is relatively The dissolving that big sodium halide may result in salt does not catch up with charge rate, thus increasing pole in charging process Change impedance.In extreme circumstances, halogenation sodium crystal can not be totally consumed within the actual charging interval. In addition the growth of cathode internal sodium halide is likely to destroy conducting metal nickel overall structure thus leading to resistance Increase.Therefore, the growth of sodium halide is considered as nickel-sodium chloride battery performance degradation and capacitance loss One major reason.
Accordingly, it would be desirable to a kind of new cathode material composition that can slow down wherein halogenide over-dimension growth And corresponding battery.
Content of the invention
On the one hand, a kind of cathode components include at least one electroactive metal, at least one alkali metal The metal-oxide of halogenide, at least one electrolyte and electrochemicaUy inert, wherein said electrochemistry Inert metal-oxide does not contain and can carry out the cation of ion exchange in electrochemical process and it is average Particle diameter is at 0.01 micron to 100 microns.
On the other hand, a kind of energy storing device include first chamber, include cathode components second chamber, And it is located at the barrier film between first chamber and second chamber.Described cathode components include at least one electrification Learn active metal, at least one alkali halide, at least one electrolyte and electrochemicaUy inert Metal-oxide, the metal-oxide of wherein said electrochemicaUy inert does not contain and can enter in electrochemical process The cation of row ion exchange and its mean diameter is at 0.01 micron to 100 microns.
On the other hand, a kind of method manufacturing energy storing device includes providing a shell, its inner surface Determine corresponding volume.Methods described also include by barrier film place in the housing, wherein said every Film has first surface and second surface, and described first surface defines at least a portion of first chamber, Described second surface defines at least a portion of second chamber, described first chamber and described second chamber Between communicate via described barrier film ion.Methods described also includes for cathode components being placed on described second chamber Room, wherein said cathode components include at least one electroactive metal, at least one alkali metal halogenation The metal-oxide of thing, at least one electrolyte and electrochemicaUy inert, the gold of described electrochemicaUy inert Belong to oxide and do not contain and can carry out the cation of ion exchange in electrochemical process and its mean diameter exists 0.01 micron to 100 microns.
Brief description
When reading described in detail below referring to the drawings, these and other features of the invention, aspect and excellent Point will become better understood, and in the accompanying drawings, identical element numbers are used for representing identical in whole accompanying drawings Part, wherein：
Fig. 1 shows that the cross section of the part of electrochemical single battery of one embodiment of the present of invention shows It is intended to.
Fig. 2 shows the cross section of the part of electrochemical single battery of an alternative embodiment of the invention Schematic diagram.
Fig. 3 shows and characterizes the schematic diagram that the discharge capacity of circulation changes with cycle-index.
Fig. 4 shows and recharges the schematic diagram that capacity changes with cycle-index.
Specific embodiment
The specific embodiment of the present invention be related to cathode components, using this cathode components energy storing device with And the method manufacturing this energy storing device, wherein said cathode components mainly include electroactive metal, Alkali-metal halogenide and be used for slow down the growth of crystal of this alkali-metal halogenide and the interpolation of roughening Agent.
Unless otherwise defined, the technical term using in the present specification and claims or section are academic Language should be has the ordinary meaning that the personage of general technical ability is understood in the technical field of the invention.This Used in description and claims, " first " or " second " and similar word be not Represent any order, quantity or importance, and be used only to distinguish different ingredients." one " Or the similar word such as " " is not offered as quantity and limits, but represents and there is at least one.Herein The language of the approximation being used can be used for quantitative expression, and showing can in the case of not changing basic function Quantity is allowed to have certain variation.Therefore, the numerical value revised with the language such as " about ", " left and right " is not It is limited to this exact value itself.Additionally, in the statement of " the about first numerical value is to second value ", " big About " revise the first numerical value and second value two values simultaneously.In some cases, approximating language can Can be relevant with the precision of measuring instrument.In the present invention, mentioned numerical value includes a unit one from low to high All numerical value that individual unit increases, it is assumed herein that interval at least two is single between any lower value and high value Unit.
The all of numerical value between minimum to peak enumerated herein, refers to when minimum and When differing more than two units between high level, obtained with a unit for increment between minimum and peak All numerical value.Such as, as temperature, air pressure, time etc. be similar to the quantity of assembly and the numerical value of process Deng when we say 1 to 90, refer to is such as 15 to 85,22 to 68,43 to 51,30 to arrive The enumerated value that 32 grades are similar to.When numerical value is less than 1, a unit can be 0.0001,0.001,0.01 Or 0.1.Merely just to illustrate as particular examples.The numeral herein including refers to what use was similar to The all possible combinations of values between a minimum value and a maximum value that method obtains.
On the one hand, embodiments of the invention are related to a kind of cathode components, and it mainly includes at least one electrification Learn active metal, at least one alkali-metal halogenide and at least one to be used for suppressing this alkali-metal The crystal seed additive that the crystal of halogenide generates.Described additive may include the electricity with suitable particle size Chemically inert metallic compound, such as, the metal-oxide of electrochemicaUy inert.When for sodium halide electricity Chi Shi, described additive can be promoted by providing inert and well-distributed crystal seed in discharge process Sodium halide homogeneous nucleation." metal-oxide of electrochemicaUy inert " as herein described refers in energy stores Under the working condition of device, stable, metal oxygen that is substantially being not involved in electrochemical reaction in cathode environment Compound.In certain embodiments, under the working condition of energy storing device, described electrochemicaUy inert The chemical composition of metal-oxide and form are held essentially constant.In some instances, described electrochemistry is lazy The metal-oxide of property substantially can not carry out ion exchange in electrochemical process, and not containing can be in electrification The cation swapping during.So " nonionic exchange oxide " also can be referred to as.
In certain embodiments, described electroactive metal be selected from titanium, vanadium, niobium, molybdenum, nickel, cobalt, Chromium, copper, manganese, silver, antimony, cadmium, stannum, lead, ferrum, zinc or combinations thereof.Specific at some In embodiment, described electroactive metal includes nickel, cobalt, chromium, copper, ferrum, zinc or their group Close.In certain embodiments, described electroactive metal includes nickel and ferrum.
In certain embodiments, suitable alkali halide is included in sodium halide, potassium halide or lithium halide At least one.In certain embodiments, suitable alkali halide include chloride, bromide, Iodide or fluoride.In certain embodiments, described cathode components include at least one sodium halide.? In some embodiments, described cathode components include at least two alkali halides.In certain embodiments, Described at least two alkali halides include sodium chloride and sodium iodide.In some further embodiments, Described alkali halide includes sodium chloride and at least one of sodium fluoride and sodium iodide.
In certain embodiments, described crystal seed additive includes the metal-oxide of electrochemicaUy inert.One In a little embodiments, the metal-oxide of described electrochemicaUy inert be selected from titanium oxide, zirconium oxide, magnesium oxide, Aluminium oxide or combinations thereof.In some specific embodiments, the metal oxygen of described electrochemicaUy inert Compound includes titanium oxide, zirconium oxide or combinations thereof.In certain embodiments, described electrochemistry Inert metal-oxide is titanium oxide.The metal-oxide of described electrochemicaUy inert is in mean diameter and grain At least one of degree distribution aspect has characteristic.In certain embodiments, the gold of described electrochemicaUy inert The mean diameter belonging to oxide is between about 0.01 micron to about 100 microns.In certain embodiments, The mean diameter of the metal-oxide of described electrochemicaUy inert about 0.01 micron to about 10 microns it Between.In certain embodiments, the mean diameter of the metal-oxide of described electrochemicaUy inert is about 0.01 Micron is between about 1 micron.
It should be noted that any have suitable dimension and inertia and stable particle in energy storage devices May serve to as crystal seed additive.Described crystal seed additive can also be its beyond metal-oxide The metallic compound of its electrochemicaUy inert.In certain embodiments, the metal compound of described electrochemicaUy inert Thing may include the slaine of electrochemicaUy inert, the sulfate such as such as barium sulfate.
In certain embodiments, described electroactive metal and alkali halide draw in the form of granules Enter to negative electrode as cathode components.In certain embodiments, described additive is described granuloplastic It is mixed in step in negative electrode, hereafter will be specifically described.Generally described additive is uniform dispersion In the granule of cathode components.
In certain embodiments, the additive metal oxide of described electrochemicaUy inert is with respect to described negative electrode The percentage by weight of component about 0.25% to 25% scope.In certain embodiments, described electrochemistry Inert additive metal oxide with respect to described cathode components percentage by weight about 0.5% to 10% Scope.
In certain embodiments, described cathode components further include electrolyte.In certain embodiments, It is filled with fused electrolyte in described cathode components.In certain embodiments, described fused electrolyte will be from Son is transferred to described cathode components from barrier film (being described below), and vice versa.Specifically real at one Apply in example, described fused electrolyte includes the binary salts such as the halogenide of such as alkali halide and aluminum.? In one specific embodiment, described fused electrolyte is sodium terachloroaluminate (NaAlCl4).Real at some Apply in example, described fused electrolyte includes extra metal halide and forms ternary or quaternary electrolyte.
Supplement to discussed above, described cathode components can include some other ingredients.For example, In addition to the aluminium element in electrolytic salt and aluminum halide, may also include in cathode components and deposit in other forms Aluminium element.In certain embodiments, described aluminum can be presented in element, such as aluminum Foil or particle.
In one embodiment, described cathode components can further include sulfur, with sulfur molecule or Containing Sulfur Presented in compound, such as metal sulfide.The metal being suitable as in described metal sulfide includes Alkali metal or transition metal.In one embodiment, described cathode components include Metal polysulfide complex. In one embodiment, described Metal polysulfide complex include ferrous disulfide, sodium disulfide, curing nickel or Person's combinations thereof.
On the one hand, embodiments of the invention are related to energy storing device.In one embodiment, described energy Amount storage device includes electrochemical single battery.Fig. 1 shows a kind of electrochemical single battery 100, tool Body ground is it is shown that the front cross-sectional view of described cell 100.Described electrochemical single battery 100 wraps Include shell 112.Described shell 112 has inner surface 114, defines certain space.Barrier film 116 is laid In shell 112.Described barrier film 116 has first surface 118, and this first surface 118 defines the first chamber Room 120 (such as, anode chamber).Described barrier film 116 has second surface 122 to define second chamber 124 (such as, cathode chamber).Barrier film can be passed through between described first chamber 120 and described second chamber 124 116 carry out ion exchange.Terminology used herein " ion exchange " refers to that ion passes through barrier film 116 first Reciprocating between chamber 120 and second chamber 124.In certain embodiments, described barrier film is permissible Alkali metal ion is transmitted between first chamber and second chamber.Suitable ionic material may include sodium, lithium Cationic form with one or more of potassium.
In the embodiment illustrated in fig. 1, second chamber 124 is located in first chamber 120.So Embodiment in, cathode chamber 124 is in anode chamber 120.In other embodiment, as Fig. 2 institute Show, first chamber 120 is located in second chamber 124.In such embodiments, anode chamber 120 In cathode chamber 124.
In one embodiment, there is anodic composition (not in figure in described first chamber or anode chamber 120 Middle display), there are cathode components 130 in described cathode chamber 124.Usually, electrochemical single battery is in base During state (uncharged state), described anode chamber 120 is empty.In cell operations, described anode Room 120 is filled with metal, and these metals flow to sun from cathode chamber 124 by barrier film 116 in the form of an ion Pole room 120.In certain embodiments, described anode chamber 120 receives and stores the anode of a container Component.Usually, described anodic composition includes alkali metal.The nonrestrictive example of described anodic composition Including lithium, sodium or potassium.Described anodic composition is typically molten state when using.In one embodiment, Described anodic composition includes sodium.
In certain embodiments, described anodic composition may include one or more additives.It is suitable for use in sun Additive in the component of pole may include metallic oxygen quencher.Described suitable metallic oxygen quencher May include one of manganese, vanadium, zirconium, aluminum or titanium or multiple.Other useful additives may include logical Cross the anodic composition of the melting material to define the membrane surface humidity of anode chamber described in increasing.
In addition, as it was previously stated, cathode components 130 are placed in second chamber 124.In some embodiments In, described cathode components 130 include at least one electroactive metal, at least one alkali metal halogenation Thing, at least one electrolyte and at least one crystal for preventing this alkali-metal halogenide are roughened Additive.Described at least one additive includes mean diameter about at 0.01 micron to 100 microns The metal-oxide of electrochemicaUy inert.
As illustrated in fig. 1 and 2, described electrochemical single battery 100 may also comprise and is placed on first chamber 120 In cathodal current catcher (also referred to as positive electrode current collector) 126/134.In certain embodiments, Described cathodal current catcher also serves as pad.As illustrated in fig. 1 and 2, also can further include to be placed on Positive pole current collector 128/136 in anode chamber 124.
On the one hand, embodiments of the invention are related to energy storage batteries.In certain embodiments, can will answer (each of which can be considered chargeable energy to several electrochemical single batteries as described herein Storage device) it is assembled into an energy storage system, such as, in battery.Multiple cells can be connected Or parallel connection is it is also possible to series connection and the mode combining in parallel connect.For convenience, can be by one group of connection Cell is referred to as module or set group.The energy grading of described module may depend on the quantity of cell With factors such as the Topology connection in module.Other factorses can be determined based on the final specific standards using.
On the one hand, as it was noted above, embodiments of the invention further relate to prepare the side of energy storing device Method.In certain embodiments, methods described includes providing a shell, and its inner surface determines corresponding Volume；Barrier film is placed in described shell, wherein said barrier film has first surface and second surface, the The one delimited at least a portion of first chamber (anode chamber), second surface defines second chamber At least a portion of (cathode chamber).Between described first chamber and described second chamber can by described every Film carries out ion exchange.
Methods described further includes to prepare cathode components (as previously mentioned), and described component is placed into In described second chamber (cathode chamber).Then can carry out also needing to carry out for the making completing described device Other steps, for example, cavity seal step and be conductively connected step, or similar.Methods described Also can further include to fill described battery or other energy stores by the circulation of a series of charging and discharging Put and be circulated, thus activation or cathode components material described in conditioning.
Example
Following examples are intended to be described in detail, should not be taken as any angle for the present invention Restriction.Unless special circumstances, all components can buy in general chemical supplier.With following The material enumerated in table 1 has made the energy storage units based on sodium chloride and nickel, wherein, case of comparative examples It is the component not having oxide addition, and sample is the component using titanium oxide as additive.
Table 1
By described cathode material, including sodium chloride (NaCl), nickel (Ni), ferrum (Fe), aluminum (Al), Sodium fluoride (NaF), sodium iodide (NaI) and iron sulfide (FeS) enter at a temperature of about 250 DEG C The row drying of 90 minutes about, is then extruded, granulated and is screened thus obtaining particle diameter in 0.325-1.5 The part of micron.Described electrolyte sodium terachloroaluminate (NaAlCl4) it is to be carried out by by sodium chloride and aluminum chloride Mixed melting obtains.Mean diameter is in 0.6 micron to 0.8 micron of titanium oxide (TiO2) powder During the step of granulation, it is added in cathode components as additive.
Each component according to table 1, can obtain an electrochemistry list similar to structure shown in Fig. 1 Body battery.For convenience of description, retouched herein with reference to figure (cell 100) and label thereon State.All cells are all in discharge condition assembling.Described diaphragm tube on described cell 100 Road 116 is made up of ceramic sodium conduction beta-alumina (beta-alumina pipeline).
Each ceramic diaphragm pipeline glass capsulation to form assembly on Alpha-alumina circle.Each group Part is all placed in stainless steel casing 112 for forming electrochemical single battery.Described beta oxidation aluminum pipe It is mounted with cathode chamber and cathode current collector in advance on road, and by the glove box full of argon Vibrosieve carries out vibration encryption to it.The beta oxidation of the vacuum environment at about 280 DEG C for the described cathode components Injection melting sodium terachloroaluminate (preparing in abovementioned steps) in aluminum tubes.After this step, described battery Cover and be soldered in glove box at a temperature of about 230 DEG C.This welding process is business electric welding system System, is purged with highly purified argon in welding process.The electrification made after this series of steps Learn cell and carry out a series of charge and discharge cycles tests, this will hereinafter be described.
Charge and discharge cycles test is with BT2000Arbin battery cycler (manufacture of Arbin company of the U.S.) With MCT100Digatron battery test system (Digatron Power electronics, inc. of U.S. system Make) come to carry out.When test, described battery first carries out just discharge and recharge, then often accelerates circulation To certain number of times, once characterized circulation.The detail parameters of this test are as shown in table 2 below.In battery Temperature be maintained at 325 DEG C in first charge and discharge cycles, in subsequent circulation, keep 295 DEG C.
Table 2
Measure the discharge capacity of each described battery.Characterizing circulation is often to accumulate in accelerating circulation Carry out after the discharge capacity of 425Ah, this provides the standardized index of battery capacity.Fig. 3 shows The described change with cycle-index for the discharge capacity characterizing circulation.As shown in figure 3, non-additive electricity The discharge capacity in circulation for the pond significantly reduces.Every 100 circulations, discharge capacity loss about 30%. And for titanium oxide as additive electrochemical single battery (sample), although initial quantity of electricity is relatively low, To replace some sodium chloride due to the addition of titanium oxide, it presents more preferable power reservoir capacity-often circulation 100 Secondary discharge capacity loss less than about 14%.Due to the difference of attenuation rate, after 25 circulations, containing oxidation The cyclic discharge capacity of the cell of titanium is higher than non-additive cell.
Fig. 4 shows and carries out accelerating to recharge the change with cycle-index for the capacity during loop test.In figure In 4, sample presents the more preferable circulation than case of comparative examples and recharges capacity stability.
This specification describes invention with specific embodiment, including optimal mode, and can help any The people being familiar with present invention process carries out experimental implementation.These operations include using any device and system and Method using any materialization.The scope of the claims of the present invention to be defined by claims, and may wrap Include other examples occurring in the art.If described other example in structure with claims Written language there is no a difference, or they have and claims description suitable structure, all by It is considered in the scope of the claim of the present invention.

Claims (10)

1. a kind of cathode components, it includes：
At least one electroactive metal；
At least one alkali halide；
At least one electrolyte；And
Do not contain the cation, mean diameter that can swap in electrochemical process to arrive at 0.01 micron The metal-oxide of 100 microns of electrochemicaUy inert.
2. cathode components as claimed in claim 1, wherein, the metal-oxide of described electrochemicaUy inert Mean diameter is at 0.01 micron to 10 microns.
3. cathode components as claimed in claim 1, wherein, the metal-oxide phase of described electrochemicaUy inert To the percentage by weight of described cathode components 0.25% to 25% scope.
4. cathode components as claimed in claim 1, wherein, described at least one electroactive metal bag Include titanium, vanadium, niobium, molybdenum, nickel, cobalt, chromium, copper, manganese, silver, antimony, cadmium, stannum, lead, ferrum, zinc, Or combinations thereof.
5. cathode components as claimed in claim 1, wherein, described at least one electroactive metal is Nickel.
6. cathode components as claimed in claim 1, wherein, described at least one alkali halide includes Sodium chloride, sodium bromide, sodium fluoride, sodium iodide or combinations thereof.
7. cathode components as claimed in claim 1, wherein, the metal of described at least one electrochemicaUy inert Oxide includes titanium oxide, zirconium oxide, magnesium oxide or combinations thereof.
8. a kind of energy storing device, including：
First chamber；
Second chamber including cathode components；And
Barrier film between first chamber and second chamber, wherein
Described cathode components include at least one electroactive metal, at least one alkali halide, At least one electrolyte and the metal-oxide of electrochemicaUy inert, the gold of wherein said electrochemicaUy inert Genus oxide does not contain the cation that can swap in electrochemical process and its mean diameter is micro- 0.01 Rice is to 100 microns.
9. energy storing device as claimed in claim 8, wherein, described barrier film includes beta-alumina.
10. a kind of method manufacturing energy storing device, including：
There is provided a shell, its inner surface determines corresponding volume；
Barrier film is placed in the housing, wherein said barrier film has first surface and second surface, institute State at least a portion that first surface defines first chamber, described second surface defines second chamber At least partially, communicate via described barrier film ion between described first chamber and described second chamber；And
Cathode components are placed on described second chamber, wherein said cathode components include at least one electrification Learn active metal, at least one alkali halide, at least one electrolyte and electrochemicaUy inert Metal-oxide, the metal-oxide of described electrochemicaUy inert does not contain can be handed in electrochemical process The cation changed and its mean diameter is at 0.01 micron to 100 microns.
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