CN106469807B - Cathode components, energy accumulating device and method - Google Patents
Cathode components, energy accumulating device and method Download PDFInfo
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- CN106469807B CN106469807B CN201510511572.0A CN201510511572A CN106469807B CN 106469807 B CN106469807 B CN 106469807B CN 201510511572 A CN201510511572 A CN 201510511572A CN 106469807 B CN106469807 B CN 106469807B
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The present invention relates to a kind of cathode components, it includes the metal oxide of at least one electroactive metal, at least one alkali halide, at least one electrolyte and electrochemicaUy inert, wherein the metal oxide of the electrochemicaUy inert does not contain the cation that can carry out ion exchange in electrochemical process and its average grain diameter at 0.01 micron to 100 microns.The invention further relates to use the energy storage device of the cathode components and manufacture the method for the energy storage device.
Description
Technical field
This invention relates generally to a kind of electrode material components, more particularly, to a kind of cathode components, using the cathode
The energy storage device of component and the method for preparing the energy storage device.
Background technique
Sodium-metal halide battery, such as sodium-metal chloride battery (sodium metal chloride
Batteries), it is considered to be the very big energy accumulating device of development potentiality, because their voltages are high, theoretical specific energy is high,
Application environment is extensive and highly-safe.Sodium-metal halide battery generally comprise molten metal cathode (commonly referred to as anode),
For the anode (commonly referred to as cathode) of electronics is stored or supplied in battery charging and discharging and is used as between anode and cathode
The solid electrolyte of " diaphragm ".Sodium-metal halide battery is usually in the discharged condition with sodium halide and electro-chemical activity gold
Belonging to nickel such as is two main materials made of cathode assembling.During the charging process, the electroactive metal is in negative pole part
Divide and is oxidized to be formed metal halide, and sodium ion is transferred to anode by electrolyte and is reduced into metal.
For example, sodium-nickel chloride battery is in the discharged condition using sodium chloride and nickel as two kinds of primary active materials, in yin
Pole assembles.The cathode material is immersed in sodium terachloroaluminate (NaAlCl4), when operating temperature range is at 260 DEG C to 340 DEG C
When, the sodium terachloroaluminate has very strong conductibility to sodium ion.During the charging process, metallic nickel is in cathode portion by oxygen
Change, and sodium ion is transferred to anode by electrolyte and is reduced into metal.Basic electrochemical reaction can be by following formula subrepresentation:
Ni+2NaCl→NiCl2+2Na
When electric discharge, sodium is transferred to cathode from anode to regenerate sodium halide.In the case where low discharge rate-fixed
Using when mostly be such case, existing sodium halide (such as sodium chloride) crystal tends to the nucleus of new crystal regrowth.
The longer the halogenation sodium crystal that long-term electrochemistry circulation results in cell cathode in such a situa-tion the bigger.This process is claimed
For " roughening " or " curing ".Halogenation sodium crystal original dimensions are less than 100 microns, and size can be increased to constantly several in cyclic process
Millimeter.The dissolution that the biggish sodium halide of crystalline size may result in salt does not catch up with charge rate, to increase during the charging process
Hyper polarization impedance.In extreme circumstances, halogenation sodium crystal can not be totally consumed within the actual charging time.This outer cathode
The growth of internal sodium halide may also can destroy conductive metal nickel overall structure so as to cause the increase of resistance.Therefore, sodium halide
Growth be considered as nickel-sodium chloride battery performance degradation and capacitance loss a major reason.
It is formed therefore, it is necessary to the new cathode material that one kind can slow down wherein halide over-dimension growth and corresponding
Battery.
Summary of the invention
On the one hand, a kind of cathode components include at least one electroactive metal, at least one alkali halide, extremely
The metal oxide of a kind of few electrolyte and electrochemicaUy inert, wherein the metal oxide of the electrochemicaUy inert does not contain
The cation that can carry out ion exchange in electrochemical process and its average grain diameter is at 0.01 micron to 100 microns.
On the other hand, a kind of energy storage device includes first chamber, the second chamber including cathode components and is located at
Diaphragm between first chamber and second chamber.The cathode components include at least one electroactive metal, at least one
The metal oxide of alkali halide, at least one electrolyte and electrochemicaUy inert, wherein the gold of the electrochemicaUy inert
Belong to oxide and does not contain the cation that can carry out ion exchange in electrochemical process and its average grain diameter at 0.01 micron to 100
Micron.
On the other hand, a kind of method manufacturing energy storage device includes providing a shell, and inner surface has determined pair
The volume answered.The method also includes placing in the housing diaphragm, wherein the diaphragm has first surface and second
Surface, the first surface define at least part of first chamber, and the second surface defines second chamber at least
A part communicates between the first chamber and the second chamber via the diaphragm ion.The method also includes will be negative
Pole component is placed on the second chamber, wherein the cathode components include at least one electroactive metal, at least one
The metal oxide of alkali halide, at least one electrolyte and electrochemicaUy inert, the metal oxygen of the electrochemicaUy inert
Compound does not contain the cation that ion exchange can be carried out in electrochemical process and its average grain diameter is micro- to 100 at 0.01 micron
Rice.
Detailed description of the invention
When reading described in detail below referring to attached drawing, these and other features of the invention, aspect and advantage will become
It is best understood from, in the accompanying drawings, identical element numbers are used to indicate identical component in all the attached drawings, in which:
Fig. 1 shows the cross-sectional view of a part of the electrochemical single battery of one embodiment of the present of invention.
Fig. 2 shows the cross-sectional view of a part of the electrochemical single battery of another embodiment of the invention.
Fig. 3 shows the schematic diagram that the discharge capacity of characterization circulation changes with cycle-index.
Fig. 4, which is shown, recharges the schematic diagram that capacity changes with cycle-index.
Specific embodiment
Specific embodiments of the present invention are related to cathode components, are somebody's turn to do using the energy storage device and manufacture of the cathode components
The method of energy storage device, wherein the cathode components mainly include electroactive metal, the halide of alkali metal and use
Come slow down the alkali metal halide crystal growth and roughening additive.
Unless otherwise defined, the technical term or scientific term used in the present specification and claims is should be
The ordinary meaning that personage in the technical field of the invention with general technical ability is understood.This specification and claims
Used in " first " either " second " and similar word are not offered as any sequence, quantity or importance, and be
For distinguishing different component parts.The similar word such as "one" or " one " is not offered as quantity limitation, but indicates exist
At least one.The language of approximation used herein can be used for quantitative expression, show the case where not changing basic function
Permissible quantity has certain variation down.Therefore, the accurate number is not limited to the modified numerical value of the language such as " about ", " left and right " institute
Value itself.In addition, " about " corrects the first numerical value and the second number simultaneously in the statement of " the about first numerical value to second value "
It is worth two values.In some cases, approximating language may be related with the precision of measuring instrument.Number mentioned in the present invention
Value includes the increased all numerical value of one unit of a unit from low to high, it is assumed herein that between any lower value and high value
Every Unit at least two.
All numerical value between minimum to peak enumerated herein, refer to when between minimum and peak
When differing two units or more, all numerical value for being obtained using a unit as increment between minimum and peak.For example, as temperature
The quantity of the similar component such as degree, air pressure, time and the numerical value of process etc., when we say 1 to 90, reference is such as 15 to arrive
85, the similar enumerated value such as 22 to 68,43 to 51,30 to 32.When numerical value is less than 1, a unit can be 0.0001,
0.001,0.01 or 0.1.Here only illustrate as particular examples.The number enumerated herein refers to similar side
The all possible combinations of values between a minimum value and a maximum value that method obtains.
On the one hand, the embodiment of the present invention is related to a kind of cathode components, mainly includes at least one electro-chemical activity gold
Belong to, the crystalline substance of the crystal generation of the halide of at least one alkali metal and at least one halide for inhibiting the alkali metal
Kind additive.The additive may include the metallic compound with the electrochemicaUy inert of suitable particle size, for example, electrochemistry
Inert metal oxide.When be used for halogenation sode cell when, the additive can by provide during discharge it is inert and
Well-distributed crystal seed promotes sodium halide homogeneous nucleation." metal oxide of electrochemicaUy inert " as described herein refers in energy
Under the operating condition for measuring storage device, metal oxide that is stable in cathode environment, being not involved in electrochemical reaction substantially.In
In some embodiments, under the operating condition of energy storage device, the chemical composition of the metal oxide of the electrochemicaUy inert
It is held essentially constant with form.In some instances, the metal oxide of the electrochemicaUy inert substantially can not be in electrochemistry
Ion exchange is carried out in the process, without containing the cation that can be swapped in electrochemical process.So can also be referred to as " non-
Ion exchange oxide ".
In some embodiments, the electroactive metal be selected from titanium, vanadium, niobium, molybdenum, nickel, cobalt, chromium, copper, manganese, silver,
Antimony, cadmium, tin, lead, iron, zinc or their combination.In some specific embodiments, the electroactive metal includes
Nickel, cobalt, chromium, copper, iron, zinc or their combination.In certain embodiments, the electroactive metal include nickel and
Iron.
In some embodiments, suitable alkali halide includes at least one in sodium halide, potassium halide or lithium halide
It is a.In some embodiments, suitable alkali halide includes chloride, bromide, iodide or fluoride.In some realities
It applies in example, the cathode components include at least one sodium halide.In some embodiments, the cathode components include at least two
Alkali halide.In some embodiments, at least two alkali halide includes sodium chloride and sodium iodide.Some
In further embodiment, the alkali halide includes sodium chloride and at least one of sodium fluoride and sodium iodide.
In some embodiments, the crystal seed additive includes the metal oxide of electrochemicaUy inert.In some embodiments
In, the metal oxide of the electrochemicaUy inert is selected from titanium oxide, zirconium oxide, magnesia, aluminium oxide or their combination.In
In some specific embodiments, the metal oxide of the electrochemicaUy inert includes titanium oxide, zirconium oxide or their combination.
In certain embodiments, the metal oxide of the electrochemicaUy inert is titanium oxide.The metal of the electrochemicaUy inert aoxidizes
Object has characteristic in terms of at least one of average grain diameter and size distribution.In some embodiments, the electrochemicaUy inert
Metal oxide average grain diameter between about 0.01 micron to about 100 microns.In some embodiments, the electrification
The average grain diameter of inert metal oxide is learned between about 0.01 micron to about 10 microns.In some embodiments, institute
The average grain diameter of the metal oxide of electrochemicaUy inert is stated between about 0.01 micron to about 1 micron.
There are suitable dimension and in energy storage devices inertia and stable particle can be used it should be noted that any
As crystal seed additive.The crystal seed additive is also possible to the metallization of other electrochemicaUy inerts other than metal oxide
Close object.In some embodiments, the metallic compound of the electrochemicaUy inert may include the metal salt of electrochemicaUy inert, such as sulphur
The sulfate such as sour barium.
In some embodiments, the electroactive metal and alkali halide are introduced into cathode in the form of granules
As cathode components.In some embodiments, the additive was mixed into cathode in the step of particle is formed,
It will hereafter be specifically described.The usual additive is uniformly dispersed in the particle of cathode components.
In some embodiments, weight of the additive metal oxide of the electrochemicaUy inert relative to the cathode components
Measure percentage about 0.25% to 25% range.In some embodiments, the metal oxide addition of the electrochemicaUy inert
Agent relative to the cathode components weight percent about 0.5% to 10% range.
In some embodiments, the cathode components further comprise electrolyte.In some embodiments, the cathode sets
Fused electrolyte is filled in point.In some embodiments, the fused electrolyte passes ion from diaphragm (being described below)
Defeated to arrive the cathode components, vice versa.In a specific embodiment, the fused electrolyte includes such as alkali metal halogen
The binary salts such as the halide of compound and aluminium.In a specific embodiment, the fused electrolyte is sodium terachloroaluminate
(NaAlCl4).In some embodiments, the fused electrolyte includes additional metal halide and forms ternary or quaternary
Electrolyte.
It supplements discussed above, the cathode components may include some other component parts.For example, in addition to electrolysis
It may also include existing aluminium element in other forms except aluminium element in matter salt and aluminum halide, in cathode components.In some realities
It applies in example, the aluminium can be to be existed in the form of element, such as the sheet metal or particle of aluminium.
In one embodiment, the cathode components can further comprise sulphur, with sulfur molecule or sulfur-containing compound, such as
The form of metal sulfide exists.The metal being suitable as in the metal sulfide includes alkali metal or transition metal.In
In one embodiment, the cathode components include Metal polysulfide complex.In one embodiment, the Metal polysulfide complex includes
Ferrous disulfide, sodium disulfide, curing nickel or their combination.
On the one hand, the embodiment of the present invention is related to energy storage device.In one embodiment, the energy storage device
Including electrochemical single battery.Fig. 1 shows a kind of electrochemical single battery 100, specifically, it is shown that the single battery
100 front cross-sectional view.The electrochemical single battery 100 includes shell 112.The shell 112 has inner surface 114, defines
Certain space.Diaphragm 116 is placed in shell 112.The diaphragm 116 has first surface 118,118 boundary of first surface
First chamber 120 (for example, anode chamber) is determined.The diaphragm 116 have second surface 122 define second chamber 124 (for example,
Cathode chamber).Between the first chamber 120 and the second chamber 124 ion exchange can be carried out by diaphragm 116.This place
Refer to that ion passes through round-trip of the diaphragm 116 between first chamber 120 and second chamber 124 with term " ion exchange ".
In some embodiments, the diaphragm can transmit alkali metal ion between first chamber and second chamber.Suitable ion
Material may include the cationic form of one or more of sodium, lithium and potassium.
In the embodiment illustrated in fig. 1, second chamber 124 is located in first chamber 120.In such embodiments,
Cathode chamber 124 is in anode chamber 120.In other embodiments, as shown in Fig. 2, first chamber 120 is located in second chamber
In 124.In such embodiments, anode chamber 120 is in cathode chamber 124.
In one embodiment, there are anodic composition (not shown in the diagram), institute in the first chamber or anode chamber 120
Stating has cathode components 130 in cathode chamber 124.Generally, electrochemical single battery is in ground state (uncharged state) Shi Suoshu anode
Room 120 is empty.In cell operations, the anode chamber 120 is filled with metal, these metals are in the form of an ion from cathode
Room 124 by diaphragm 116 flow to anode chamber 120 come.In some embodiments, the anode chamber 120 receives and stores an appearance
The anodic composition of device.Generally, the anodic composition includes alkali metal.The unrestricted example of the anodic composition includes
Lithium, sodium or potassium.The anodic composition is usually molten state when in use.In one embodiment, the anodic composition includes sodium.
In some embodiments, the anodic composition may include one or more additives.It is suitable for use in anodic composition
Additive may include metallicity oxygen quencher.The oxygen quencher of the suitable metallicity may include manganese, vanadium, zirconium, aluminium or
One or more in titanium.Other useful additives may include increasing described to define sun by the anodic composition of melting
The material of the membrane surface humidity of pole room.
In addition, as previously mentioned, cathode components 130 are placed in second chamber 124.In some embodiments, the cathode
Component 130 includes at least one electroactive metal, at least one alkali halide, at least one electrolyte, Yi Jizhi
A kind of few additive for preventing the crystal of the halide of the alkali metal to be roughened.At least one additive includes average grain
Diameter is about in the metal oxide of 0.01 micron to 100 microns of electrochemicaUy inert.
As illustrated in fig. 1 and 2, the electrochemical single battery 100 may also comprise the negative electricity being placed in first chamber 120
Flow collector (also referred to as positive electrode current collector) 126/134.In some embodiments, the cathodal current collector also serves as
Gasket.It as illustrated in fig. 1 and 2, can also further comprise the positive current collector 128/136 being placed in anode chamber 124.
On the one hand, the embodiment of the present invention is related to energy storage batteries.It in some embodiments, can be by a plurality of as herein
The electrochemical single battery (each of them can be considered as chargeable energy storage device) is assembled into an energy
Storage system is measured, for example, in battery.Multiple single batteries can serial or parallel connection, can also connect and the mode combined in parallel connects
It connects.For convenience, the single battery of one group of connection can be known as to module or set group.The energy grading of the module can be depended on
In factors such as Topology connections in the quantity and module of single battery.Other factors can be true based on the specific standards finally used
It is fixed.
On the one hand, as it was noted above, the method that the embodiment of the present invention further relates to prepare energy storage device.Some
In embodiment, the method includes providing a shell, inner surface has determined corresponding volume；Diaphragm is placed into described outer
In shell, wherein the diaphragm has first surface and second surface, first surface defines at least the one of first chamber (anode chamber)
Part, second surface define at least part of second chamber (cathode chamber).The first chamber and the second chamber it
Between can pass through the diaphragm carry out ion exchange.
The method further includes preparing cathode components (as previously described), and the component is placed into described second
In chamber (cathode chamber).Then it can carry out in order to complete the production of described device also and need the other steps carried out, for example, chamber is close
It seals step and is conductively connected step or similar.The method can also further comprise by a series of charging and discharging
Circulation recycles the battery or other energy storage devices, thus cathode components material described in activation or conditioning.
Example
Following examples are intended to be described in detail, should not be taken as any angle for limitation of the invention.
Unless special circumstances, all components can be bought in general chemical supplier.It is made of material that being enumerated in following table 1
Energy storage units based on sodium chloride and nickel, wherein case of comparative examples is the component of not oxide addition, and sample be with
Component of the titanium oxide as additive.
Table 1
By the cathode material, including sodium chloride (NaCl), nickel (Ni), iron (Fe), aluminium (Al), sodium fluoride (NaF), iodate
Sodium (NaI) and iron sulfide (FeS) about 250 DEG C at a temperature of carry out drying in 90 minutes or so, then squeezed,
Granulation and screening are to obtain part of the partial size at 0.325-1.5 microns.Electrolyte sodium terachloroaluminate (the NaAlCl4) be by
Sodium chloride and aluminium chloride are carried out what mixed melting obtained.Titanium oxide (TiO of the average grain diameter at 0.6 micron to 0.8 micron2) powder
End is added in cathode components in the step of granulating as additive.
Each component according to table 1 can get the electrochemical single battery for being similar to structure shown in Fig. 1.For
Convenient for explanation, label herein with reference to figure (single battery 100) and thereon is described.All single batteries are all to discharge
State assembling.The diaphragm pipeline 116 on the single battery 100 is by ceramic sodium conduction beta-alumina (beta-alumina pipeline)
It is made.
Component is formed on each ceramic diaphragm pipeline glass capsulation to Alpha-alumina circle.Each component is put
It sets and is used to form electrochemical single battery in stainless steel casing 112.It is mounted with cathode chamber in advance on the beta-alumina pipeline
And cathode current collector, and vibration encryption is carried out to it by the vibrating screen in the glove box full of argon gas.The cathode
Component is injected melting sodium terachloroaluminate in the beta-alumina pipeline of about 280 DEG C of vacuum environment and (is made in abovementioned steps
It is standby).After the step, the battery cover about 230 DEG C at a temperature of be soldered in glove box.The welding process is
Business electric arc welding system is purged with the argon gas of high-purity in welding process.The manufactured electrochemistry after this series of steps
Single battery carries out a series of charge and discharge cycles tests, this will hereinafter be described.
Charge and discharge cycles test be with BT2000Arbin battery cycler (Arbin company, the U.S. manufactures) and
MCT100Digatron battery test system (manufacture of Digatron Power electronics, inc., the U.S.) Lai Jinhang's.In
When test, the battery first carries out just charge and discharge, and then every acceleration is recycled to certain number, carries out primary characterization circulation.
The detail parameters of the test are as shown in table 2 below.Temperature in battery is maintained at 325 DEG C in first charge and discharge cycles, subsequent
In circulation, kept for 295 DEG C.
Table 2
Measure the discharge capacity of each battery.Characterization circulation is the electric discharge of every accumulation 425Ah in accelerating circulation
It is carried out after capacity, this provides the standardized index of battery capacity.Fig. 3 show it is described characterization circulation discharge capacity with
The variation of cycle-index.As shown in figure 3, discharge capacity of the additive-free battery in circulation significantly reduces.It follows for every 100 times
Ring, discharge capacity loss about 30%.And the electrochemical single battery (sample) for titanium oxide as additive, although initially
Electricity is lower, but replaces some sodium chloride due to being added to titanium oxide, presents the every circulation 100 of better power reservoir capacity-
Secondary discharge capacity loss less than about 14%.Due to the difference of attenuation rate, after 25 times recycle, the single battery containing titanium oxide
Cyclic discharge capacity is higher than additive-free single battery.
Fig. 4 shows the variation for carrying out recharging capacity with cycle-index when acceleration loop test.In Fig. 4, sample
It presents circulation more better than case of comparative examples and recharges capacity stability.
This specification is described to invent with specific embodiment, including optimal mode, and can help any to be familiar with this hair
The people of bright technique carries out experimental implementation.These operations include using any device and system and using the side of any materialization
Method.The scope of the patents of the invention is defined by claims, and may include other examples occurred in the art.Such as
Other examples described in fruit are in structure from the written language of claims that different or they have and claims
The comparable structure of description, is considered as in the scope of the claims of the invention.
Claims (16)
1. a kind of cathode components comprising:
At least one electroactive metal；
At least one alkali halide；
At least one electrolyte；And
The crystal seed additive of at least one crystal growth for inhibiting the alkali halide, the crystal seed additive include flat
Metallic compound of the equal partial size in 0.01 micron to 100 microns of electrochemicaUy inert, wherein the metallization of the electrochemicaUy inert
Closing object includes titanium oxide, zirconium oxide, magnesia, barium sulfate or their combination.
2. cathode components as described in claim 1, wherein the average grain diameter of the metallic compound of the electrochemicaUy inert is 0.01
Micron is to 10 microns.
3. cathode components as described in claim 1, wherein the relatively described cathode components of the metallic compound of the electrochemicaUy inert
Range of the weight percent 0.25% to 25%.
4. cathode components as described in claim 1, wherein it is described at least one electroactive metal include titanium, vanadium, niobium, molybdenum,
Nickel, cobalt, chromium, copper, manganese, silver, antimony, cadmium, tin, lead, iron, zinc or their combination.
5. cathode components as described in claim 1, wherein at least one electroactive metal is nickel.
6. cathode components as described in claim 1, wherein it is described at least one alkali halide include sodium chloride, sodium bromide,
Sodium fluoride, sodium iodide or their combination.
7. cathode components as described in claim 1, wherein the metallic compound of the electrochemicaUy inert includes titanium oxide, oxidation
Zirconium, magnesia or their combination.
8. a kind of energy storage device, comprising:
First chamber；
Second chamber including cathode components；And
Diaphragm between first chamber and second chamber, wherein
The cathode components include at least one electroactive metal, at least one alkali halide, at least one electrolysis
The crystal seed additive of matter and at least one crystal growth for inhibiting the alkali halide, the crystal seed additive packet
Average grain diameter is included in the metallic compound of 0.01 micron to 100 microns of electrochemicaUy inert, wherein the gold of the electrochemicaUy inert
Belonging to compound includes titanium oxide, zirconium oxide, magnesia, barium sulfate or their combination.
9. energy storage device as claimed in claim 8, wherein the diaphragm includes beta-alumina.
10. energy storage device as claimed in claim 8, wherein the average grain diameter of the metallic compound of the electrochemicaUy inert
At 0.01 micron to 10 microns.
11. energy storage device as claimed in claim 8, wherein the relatively described yin of the metallic compound of the electrochemicaUy inert
Range of the weight percent of pole component 0.25% to 25%.
12. energy storage device as claimed in claim 8, wherein the metallic compound of the electrochemicaUy inert include titanium oxide,
Zirconium oxide, magnesia or their combination.
13. a kind of method for manufacturing energy storage device, comprising:
A shell is provided, inner surface has determined corresponding volume；
Diaphragm is placed in the housing, wherein the diaphragm has first surface and second surface, first surface circle
At least part of first chamber is determined, the second surface defines at least part of second chamber, the first chamber
It is communicated between the second chamber via the diaphragm ion；And cathode components are placed on the second chamber, wherein institute
State cathode components include at least one electroactive metal, at least one alkali halide, at least one electrolyte and
The crystal seed additive of at least one crystal growth for inhibiting the alkali halide, the crystal seed additive include average grain
Metallic compound of the diameter in 0.01 micron to 100 microns of electrochemicaUy inert, wherein the metallic compound of the electrochemicaUy inert
Including titanium oxide, zirconium oxide, magnesia, barium sulfate or their combination.
14. method as claimed in claim 13, wherein the average grain diameter of the metallic compound of the electrochemicaUy inert is micro- 0.01
Rice is to 10 microns.
15. method as claimed in claim 13, wherein the relatively described cathode components of the metallic compound of the electrochemicaUy inert
Range of the weight percent 0.25% to 25%.
16. method as claimed in claim 13, wherein the metallic compound of the electrochemicaUy inert include titanium oxide, zirconium oxide,
Magnesia or their combination.
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