CN103779541A - Nanostructured materials for electrochemical conversion reactions - Google Patents

Nanostructured materials for electrochemical conversion reactions Download PDF

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Publication number
CN103779541A
CN103779541A CN201310302774.5A CN201310302774A CN103779541A CN 103779541 A CN103779541 A CN 103779541A CN 201310302774 A CN201310302774 A CN 201310302774A CN 103779541 A CN103779541 A CN 103779541A
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lithium
metal
particle
negative electrode
component
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CN103779541B (en
Inventor
蒂莫西·霍姆
贾格迪普·辛格
雷纳·法兴
约瑟夫·哈恩
韦斯顿·阿瑟·赫尔曼
程偕召
布拉德利·O·斯廷森
卡尔·布朗
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Kundenskop battery Co.
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Quantumscape Corp
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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 disclosure is related to battery systems. More specifically, embodiments of the disclosure provide a nanostructured conversion material for use as the active material in battery cathodes. In an implementation, a nanostructured conversion material is a glassy material and includes a metal material, one or more oxidizing species, and a reducing cation species mixed at a scale of less than 1 nm. The glassy conversion material is substantially homogeneous within a volume of 1000nm3.

Description

For the nano structural material of electro-chemical conversion reaction
Technical field
The disclosure relates to battery system.
Background technology
In recent years, affect due to the shortage of the energy based on fossil fuel and from the adverse environment of Fossil fuel consumption, the public department with privately owned all puts into the resource of a large amount of preciousnesses in clean energy technology.An importance of clean energy technology is energy storage, or battery system briefly.In the past, develop and used many battery types, they have its merits and demerits separately.Due to the chemical property of lithium material, comprise high charge density, so lithium material has been used in the multiple parts of battery.For example, in chargeable lithium ion battery, in discharge process, lithium ion moves to positive pole from negative pole.Substantially in service at lithium battery, the conversion reaction of transition material experience and lithium, the performance of transition material is an importance of battery.
Summary of the invention
An aspect of the present disclosure relates to cathode material, and its feature can be for having particle or the nanometer farmland of about 20nm or less intermediate value characteristic size.These particles or nanometer farmland comprise particle or the nanometer farmland of the metal of (i) chosen from Fe, cobalt, manganese, copper, nickel, bismuth and alloy thereof, and (ii) particle or the nanometer farmland of the fluoride of lithium.
In some embodiments, individual particle wraps metallic fluoride extraly.In some cases, cathode material comprises the fluoride of iron, for example ferric flouride extraly.For example, metal can be iron, and particle or nanometer farmland further comprise ferric flouride.
In some embodiments, metal is only contained on some particles or nanometer farmland, and the fluoride of lithium is only contained on other particles or nanometer farmland.In some embodiments, the fluoride that the individual particle of cathode material comprises metal and lithium.In an example, the fluoride of lithium comprises oxygen lithium fluoride.
In some embodiments, cathode material comprises (iii) conductive additive extraly.In some cases, conductive additive is the ion-electron conductor mixing.In some cases, conductive additive is lithium ion conductor.In some embodiments, lithium ion conductor is or comprises sulfo--LiSICON, garnet, lithium sulfide, FeS, FeS 2, the sulfide of copper, the sulfide of titanium, Li 2s-P 2s 5, the sulfide of lithium iron, Li 2s-SiS 2, Li 2s-SiS 2-LiI, Li 2s-SiS 2-Al 2s 3, Li 2s-SiS 2-GeS 2, Li 2s-SiS 2-P 2s 5, Li 2s-P 2s 5, Li 2s-GeS 2-Ga 2s 3or Li 10geP 2s 12.
In some embodiments, the intermediate value characteristic size on particle or nanometer farmland is about 5nm or less.In some materials, the metal in particle is rendered as the metal nano farmland with the intermediate value characteristic size that is less than about 20nm.In some materials, particle or nanometer farmland are at about 1000nm 3volume in be uniform substantially.
Another aspect of the present disclosure relates to the glassy state transition material for negative electrode.The feature of such material can be metal, one or more of oxidizing substance and the reductive cation of mixing under the size that is less than 1nm.In addition, glassy state transition material is at 1000nm 3volume in be uniform substantially.In some embodiments, cation comprises lithium, sodium or magnesium.In some embodiments, glassy state transition material does not basically contain volume and is greater than 125nm 3single metallics or the agglomerate of oxidizing substance.
Relate on the other hand negative electrode, its feature can be following characteristics: (a) collector body; (b) with the electrochemical active material of collector body electric connection.Electrochemical active material comprises (i) metal component, and (ii) the lithium compound component of mixing with metal component in about 20nm or less distance size.In addition, while forming the compound of metal component and the anion of lithium compound when charging completely, electrochemical active material has about 350mAh/g or larger reversible specific capacity in the time utilizing lithium ion to discharge with the speed at least about 200mA/g.
In some cases, negative electrode comprises conduction reinforcing agent extraly, for example electronic conductor component and/or ion conductor component.The ion-electron conductor component that some negative electrodes comprise mixing.In some cases, the ion-electron conductor component of mixing accounts for 30 % by weight that are less than of negative electrode.The example of the ion-electron conductor component of mixing comprises sulfide, FeS, the FeS of sulfo--LiSICON, garnet, lithium 2, the sulfide of copper, the sulfide of titanium, Li 2s-P 2s 5, the sulfide of lithium iron, Li 2s-SiS 2, Li 2s-SiS 2-LiI, Li 2s-SiS 2-Al 2s 3, Li 2s-SiS 2-GeS 2, Li 2s-SiS 2-P 2s 5, Li 2s-P 2s 5, Li 2s-GeS 2-Ga 2s 3and Li 10geP 2s 12.
In some negative electrodes, metal component is transition metal, aluminium, bismuth or the alloy of these metals arbitrarily.In some cases, metal component is the alloy of copper, manganese, cobalt, iron or any these metals.For example, metal component can be the alloy of iron and cobalt and/or manganese.In some negative electrodes, it is about 5nm or less metal grain that metal component comprises intermediate value characteristic length.
In some embodiments, lithium compound component is selected from the halide of lithium, the sulfide of lithium, the sulfur halide of lithium, the oxide of lithium, nitride, the phosphide of lithium and the selenides of lithium of lithium.In an example, lithium compound component is the fluoride of lithium.In another example, lithium compound component is the fluoride of lithium, and metal component is the alloy of manganese, cobalt, copper, iron or any these metals.In some negative electrodes, described lithium compound component contains intermediate value characteristic length and is of a size of about 5nm or less particle or nanometer farmland.In some embodiments, the anion that lithium compound component comprises when charging and metal formation metallic compound, described metallic compound and the reaction of lithium ion experience generate metal and lithium compound component, and the Gibbs free energy of reaction is at least about 500kJ/ mole.
Another aspect of the present disclosure relates to solid-state energy storage device, it is characterized in that following characteristic: (i) anode, (ii) solid electrolyte and (iii) negative electrode, the electrochemical active material that described (iii) negative electrode comprises (a) collector body, (b) and collector body electric connection.Electrochemical active material comprises (i) metal component, and (ii) the lithium compound component of mixing with metal group phase-splitting in about 20nm or less distance size.In addition, when utilizing lithium ion, at 50 ℃, relatively Li is between 1 to 4V during with speed electric discharge at least about 200mA/g, and electrochemical active material has about 600mAh/g or larger reversible specific capacity.
In some energy storage devices, anode, solid electrolyte provide the lamination of thickness approximately 1 μ m to 10 μ m together with negative electrode.In some designs, to provide at thickness be about 10nm in the layer of 300 μ m to electrochemical active material.
In some energy storage devices, in the time utilizing lithium ion to discharge with the speed at least about 200mA/g, electrochemical active material has about 700mAh/g or larger reversible specific capacity.In some designs, when at 100 ℃ and the charge rate of about 200mAh/g active material of cathode carry out circulation time, described device has lower than the average voltage of about 1V and lags behind.
Various other features of solid-state energy storage device are identical with those features that just target marks.These other features comprise the composition of negative electrode etc.
Another aspect of the present disclosure relates to battery unit, it is characterized in that following characteristics: (a) electrolyte; (b) anode; (c) have and the solid-state transition material at electrolytical interface, the described solid-state transition material under discharge condition is included in the metal mixing under the size that is less than 1nm, one or more of oxidizing substance and reductive cation.In some embodiments, transition material is glassy state substantially.Metal can be transition metal material, for example cobalt, copper, nickel, manganese and/or iron material.Cation can be lithium, sodium and/or magnesium material.
On the other hand, the disclosure relates to cell apparatus, it is characterized in that following characteristics: the anode region that (a) contains lithium; (b) electrolyte area; (c) cathode zone of the fluoride materials that contains the certain thickness lithium that is configured to amorphous state; (d) space is arranged in the interior multiple ferrous metal particle matters with formation lithiumation transition material of interior zone of the fluoride of certain thickness lithium.In addition, the energy density of the sign cathode zone of described cell apparatus be greater than cathode zone theoretical energy density approximately 80%.In some embodiments, more than first ferrous metal material is characterised in that diameter is about 5nm to 0.2nm.In some embodiments, the thickness of the fluoride materials of lithium is characterised in that thickness is 30nm to 0.2nm.In some cases, the thickness of the fluoride materials of lithium is uniform.In some embodiments, cathode zone is characterised in that iron: fluorine: the ratio of lithium is about 1:3:3.In some embodiments, cathode zone is characterised in that iron: fluorine: the ratio of lithium is from about 1:1.5:1.5 to 1:4.5:4.5.
Another aspect of the present disclosure relates to the method that forms transition material, and the feature of described method can be following operation: (i) provide the first precursor material, described the first precursor material contains metal material; (ii) provide the second precursor material, described the second precursor material contains reductive cation material; (iii) evaporate described the first precursor material and described the second precursor material to vapor state; (iv) in vacuum chamber, described first precursor material of mixed vapour state and the second precursor material are with at described indoor formation composite material, and described composite material contains described the first precursor material and the second precursor material that under the length dimension that is less than about 20nm, mix; (v) collect described composite material.In some embodiments, the first precursor material and the second precursor material are characterised in that the trend being separated.In some embodiments, evaporation is used thermal evaporation method, beam methods or flash evaporation to carry out.In some embodiments, described method comprises extraly with the operation at least about the 10 Kelvins cooling described composite material of speed per second.
Another aspect of the present disclosure relates to the method that forms transition material, and described method is characterised in that following operation: the first precursor material that contains metal material (i) is provided; (ii) provide the second precursor material that contains reductive cation material; (iii) melt described the first precursor material and the second precursor material to liquid; (iv) described the first precursor material and the second precursor material are ejected in cooler environment, form composite material at the first precursor material described in described cooler environment and the second precursor material, described composite material is with cooling to produce the particle being shaped at least about 100 Kelvins speed per second; (v) collect the particle being shaped.In some embodiments, the first precursor material and the second precursor material are characterised in that the trend being separated.In some embodiments, the particle of shaping is included in the first precursor material and the second precursor material that under the length dimension that is less than about 20nm, mix.
In some embodiments, cooler environment is cooling chamber.Cooling chamber can comprise cooling surface.The feature of cooling surface can be high heat conductance.In some cases, cooling comprising composite material is exposed to cryogenic gas material.
In some embodiments, described method comprises following operation extraly: the first precursor material is ejected into the public domain of cooling chamber from the first nozzle; From second nozzle, the second precursor material is ejected into the public domain of cooling chamber.
In some embodiments, described method comprises following operation extraly: combination the first precursor material and the second precursor material are to form combined material; Combined material is ejected in cooling chamber.
The melt operation of the first precursor material can carry out respectively with the fusing of the second precursor material.Described fusing can be carried out for the first precursor material and the second precursor material at different temperature.
Another aspect of the present disclosure relates to by following operation formation battery unit: (i) hold one deck cathode current collector; (ii) form the cathode zone that comprises nanostructure transition material, the nanometer farmland of the nanometer farmland of the iron that described nanostructure transition material comprises formation and the fluoride of lithium; (iii) form the solid electrolyte layer that covers described cathode zone; (iv) form the anode and/or the anode current collector that cover described solid electrolyte layer.Described nanostructure transition material can be that atom mixes.In some embodiments, described method comprises the other operation that formation and cathode current collector and anode and/or anode current collector electrically contact.
Accompanying drawing explanation
Figure 1A represents to comprise anode spaced apart by solid electrolyte and that separate and the solid-state energy storage device of negative electrode.
Figure 1B represents to have in abutting connection with the anode current collector of anode with in abutting connection with the solid-state energy storage device of the cathode current collector of negative electrode.
Fig. 2 A represents five examples of the transition material with various nanometers farmland and particle form.
Fig. 2 B represents the particle that can use in ferric flouride and relevant transition material and the other example of nanometer domain structure.
Fig. 3 schematic representation the basis material providing as pantostrat, described pantostrat has embedded the particle separating or the nanometer farmland of conduction reinforcing agent and active material.
The figure of the relation of the LiF in battery performance and layer structure that Fig. 4 represents to weigh by cathode volume energy density.
Fig. 5 is illustrated in the figure of the constant current charge electric discharge of the 3LiF+Fe negative electrode of 66nm at 120 ℃.
Fig. 6 is illustrated in the figure of the constant current charge electric discharge of the 3LiF+Fe negative electrode of 129nm at 120 ℃.
Fig. 7 represents that negative electrode is 134nm (3LiF+Fe+S 0.14) the figure of constant-current discharge of battery.
Fig. 8 represents that negative electrode is 134nm (3LiF+Fe+S 0.53) the figure of constant-current discharge of battery.
Fig. 9 provides the figure of the relation of the length dimension of the LiF material in battery performance and the layer structure of weighing by cathode volume energy density.
Figure 10 is the figure of the relation of the length dimension of the Fe in battery performance and the layer structure of weighing by cathode volume energy density.
Figure 11 provides the cross-sectional view of the nanostructure transition material in the size of about 5nm.
Figure 12 provides the cross-sectional view of the nanostructure transition material in the size of about 2nm.
Figure 13 provides the cross-sectional view of the nanostructure transition material in the size of about 2nm.
Figure 14 is the figure that illustrates nano-structured transition material and keep the example of the benefit of composition homogeneity.
Figure 15 represents the theoretical energy density of lithiumation conversion cathode material with respect to standard Li anode.
Figure 16 represents the theoretical specific energy of lithiumation conversion cathode material with respect to standard Li anode.
Figure 17 represents for the figure of initial 5 charge/discharge cycle of copper fluoride sample (voltage (measurement of relative standard's lithium electrode) is the active capacity of cathode material relatively).
Figure 18 is illustrated in the electric discharge energy of the sample that transition material contains some transition metal alloys used.
Figure 19 is the capacity of following transition material offering sample and the statistics that lags behind: FeCo+LiF, FeMn+LiF, Fe 3co+LiF and control sample Fe+LiF.
Embodiment
Foreword
The present invention is not intended to be limited to described embodiment, but goes for the widest scope consistent with principle disclosed herein and novel feature.Disclosed embodiment relates to the negative electrode that contains high-capacity material, and described high-capacity material is repeatedly being carried out to the rear high speed reversible of charging and discharging circulation redox reaction.Such material is called as " conversion " material in this article sometimes.
Conventionally, embedding and/or transition material can use in battery system.For example, cathode material can be for the embedding of lithium or conversion.The insert material that can prepare at macro-size or under nano-scale is used conventionally, and generally has lower energy density (for example, lower than about 800Wh/kg active material).On the contrary, transition material can provide much higher energy density (for example about 1000-2500Wh/kg active material).
In some embodiments, transition material comprises oxidizing substance, reductive cation material and metallics.These materials are called as composition or component in this article sometimes.Oxidizing substance is strong electronegativity element, compound or anion typically.The example of oxidizing substance anion comprises halide (fluoride, chloride, bromide and iodide), oxide and sulfide etc.Reductive cation material is electropositive element or cation typically, for example lithium, sodium, potassium or magnesium and ion thereof.The electropositivity of metallics is generally than a little less than the electropositivity of reductive cation material.Transition metal is sometimes as metallics.Example comprises cobalt, copper, nickel, manganese and iron.Transition material can contain two or more oxidizing substances, two or more reductive cation materials and/or two or more metallicses.
As understood in the art, in battery and electrode thereof the charging process in discharge process and the in the situation that of secondary cell or rechargeable battery, experience electrochemical conversion.To the charging and discharging state of particular conversion material be described now.
Discharge condition: under discharge condition, metallics is general than more reducing under charged state.For example, metallics is simple substance state or lower oxidation state or nominal price (for example+2 rather than+3).In addition, in discharge process, oxidizing substance can be removed pairing with the pairing of reductive cation material and with metallics.Further, in discharge process, reductive cation material is tending towards moving into negative electrode, and it is by oxidized with oxidizing substance pairing there.Pairing typically performance is the formation of for example covalent bond of chemical bond or ionic bond.
According to this execution mode, under discharge condition, transition material can comprise elemental metals material, one or more of oxidizing substance and reductive cation material.As an example, discharge condition can comprise for example iron of at least one elemental metals and a kind of reductive cation halide, the fluoride of for example lithium.The component of electric discharge transition material can be thoroughly to disperse each other in discharge material.As below more fully described, these materials can be under about 20nm or less size, mutually mix or disperse.
The negative electrode that should understand type described herein can exist with various charged states.In some cases, design or actuating battery make never to reach electric discharge completely.Therefore, be ferric flouride if be for example full of electric transition material, the negative electrode of " completely " electric discharge can contain the mixture of fe, lithium fluoride and some ferric flourides and possible some ferrous fluorides.The use of " electric discharge " or " discharge condition " is herein relative term, only refers to the state more discharging compared with charged state material transition material.The use of " charging " or " charged state " similarly, herein refers to the state more charging compared with corresponding discharge condition material transition material.
Charged state: under charged state, metallics is tending towards and oxidizing substance pairing, conventionally forms compound.In charging process, oxidizing substance is tending towards removing pairing and matching with metallics with reductive cation material.Reductive cation material is tending towards moving out negative electrode and moves and/or be diffused into negative pole, there they with stronger reduction-state exist (for example, as elemental metals, for example lithium metal or insert the lithium of for example carbon of matrix or silicon).
As an example, in charging process, fe can form ferric flouride and/or ferrous fluoride with fluorine anion pairing.Meanwhile, fluorine anion can for example be removed pairing lithium fluoride from reductive cation fluoride.Now free lithium cation moves and/or is diffused into negative electrode, and it is reduced into lithium metal or lithium insert material there.
No matter under charging or discharge condition, the associated electrical chemical property of the size impact material of composition in transition material.Find, compared with the transition material separating with larger distance with composition, the transition material that its composition or composition separate with the distance of very little (sometimes in atomic size rank) can have specific performance benefit.In some embodiments, described composition separates with the distance that is not more than about 20nm.These transition materials have been found to provide various benefits, the cycle life for example increasing, the efficiency of improvement, energy density, the power density of improvement and the cryogenic property of improvement of improvement.Term " nanostructure " is used to refer to the transition material under charge or discharge state sometimes, and wherein composition material is spaced with about 20nm or less size.
In some embodiments, under discharge condition, the farmland of the dispersion that transition material contains elemental metals (or its alloy) and lithium compound.In some embodiments, the crystal grain of the dispersion of metal or alloy embeds in the successive substrates of lithium compound.In other embodiments, metal or alloy and lithium compound exist with the structure of granule or other dispersions.In each case, the various components of transition material can mix and/or additionally exist with nanostructure size.Single farmland can be nanometer farmland.Nanometer farmland can have about 20nm or less or about 10nm or less or about 5nm or less average or intermediate value characteristic size.Use ferric flouride as example transition material, under discharge condition, nanometer farmland can be mainly iron and lithium fluoride.Under charged state, nanometer farmland is mainly ferric flouride.Under two kinds of charged states, nanometer farmland can be crystallization or unbodied/glassy state.Farmland can be composition (for example only containing metallics) or inhomogeneous (for example, constituting by metallics, oxidizing substance and reductive cation material) uniformly.
In various embodiments, form or mix transition material its composition is separated in about 1nm or less size.The feature of some these type of materials can be glassy state or unbodied.Vitreous material can be regarded amorphous, composition substantially as and substantially lack uniformly and substantially the material of long-range order.In some instances, glassy state transition material is at 1000nm 3volume in be uniformly (on composition and/or in form) substantially.
Transition material for example, is structurized at nanometer level (length is less than 20nm).In an example, the FeF in the transition material of charging 3the feature of molecule can be glassy state or unbodied structure and be uniform substantially.In some instances, under discharge condition, transition material can comprise the glass transition compound of lithium, sodium and/or magnesium.So glassy state or unbodied structure can be provided as particle, layer etc.In these particles or layer, the distance of the length dimension that composition metal, oxidizing substance and reductive cation material are marked to be not more than is fifty-fifty spaced.In some cases, the particle that has glassy state or amorphous state is not reunited substantially.In other cases, at least some granulateds become aggregate.
According to this execution mode, under discharge condition, transition material can be included in the metal material separating in the size that is less than about 20nm, one or more of oxidizing substance and reductive cation material.More specifically, transition material is at about 1000nm 3or in less volume, be substantially uniform.In an example, the molecule that comprises metal, oxidizing substance and reductive cation is structurized on nano-scale.As above-mentioned example presents, discharge material can comprise the compound of the simple substance form of metallics and the anion of reducing metal cation and oxidizing substance.
Under charged state, the compound that transition material contains metal.In some embodiments, can not consider that in the electrochemical charge-exoelectrical reaction of negative electrode stoichiometric proportion following formula represents:
M + LiX ↔ MX + Li + + e -
Wherein M is metallics, and X is oxidizing substance; For example, element is as the anion of the combination of halogen, oxygen, sulphur, phosphorus, nitrogen, selenium or these elements or electron rich material.In concrete example, oxidizing substance is the combination (for example fluoride and sulfide) of halogen ion and chalcogen ion.In some variant of above-mentioned chemical equation, lithium is by sodium, potassium, magnesium or other electropositive metal ion substitutions.
The metallic compound MX existing in the cathode material of charging should react with lithium ion according to the discharge path of above formula.Typically, in the time considering complete cell reaction Li+MX → LiX+M, exoelectrical reaction is relevant with suitably large Gibbs free energy.Gibbs free energy is by Δ G rxn=-E*n*F is corresponding to the cell voltage of reaction, and wherein E is voltage, and n is the electron number of reaction, and F is Faraday constant.In some embodiments, the Gibbs free energy of reaction is at least about 500kJ/ mole or at least about 750kJ/ mole or at least about 1MJ/ mole.
In some embodiments, the voltage of complete completely charged negative electrode is at least about 2.0V with respect to metal lithium electrode, or be at least about 3.0V with respect to metal lithium electrode, or be at least about 4.0V with respect to metal lithium electrode, or be at least about 4.5V with respect to metal lithium electrode.
Under charged state, negative electrode transition material can keep the gross morphology feature existing under discharge condition.These features comprise composition separation distance (such as particle or crystalline size), basal body structure (such as glassy state) etc.In some cases, material can expand under discharge condition.According to material, change in volume can be about 5% or larger or about 10% or larger.
The example of suitable metallics M comprises transition metal, aluminium and bismuth.In some cases, metal is selected from the first row transition metal.The instantiation of operable transition metal comprises vanadium, chromium, copper, iron, cobalt, manganese, nickel, ruthenium, titanium, silver and tungsten.Also can use the alloy of these metals.The example of these alloys comprises the alloy of iron and cobalt formation and the alloy of iron and manganese formation.The example of suitable oxidizing substance anion X comprises O, S, N, P, F, Se, Cl, I and its combination.
The example of suitable charged state cathode material comprises sulfide, oxide, halide, phosphide, nitride, chalcogenide, oxysulfide, oxygen fluoride, sulphur-fluoride and sulphur-oxygen fluoride.In various embodiments, the transition material of charging comprises one or more of following materials: AgF; AlF 3; BiF 3; B 2o 3; Co 3o 4; CoO; CoS 2; Co 0.92s; Co 3s 4; Co 9s 8; CoN; Co 3n; CoP 3; CoF 2; CoF 3; Cr 2o 3; Cr 3o 4; CrS; CrN; CrF 3; CuO; Cu 2o; CuS; Cu 2s; CuP 2; Cu 3p; CuF 2; Fe 2o 3; FeO; FeOF; FeS 2; FeS; Fe 2s 2f 3; Fe 3n; FeP; FeF 2, FeF 3; FeOF; Ga 2o 3; GeO 2; MnO 2; Mn 2o 3; Mn 2o 5; MnO; MnS; MnS 2; MnP 4; MnF 2, MnF 3, MnF 4, MoO 3; MoO 2; MoS 2; Nb 2o 5; NiO; NiS 2; NiS; Ni 3s 2; Ni 3n; NiP 3; NiP 2; Ni 3p; NiF 2; PbO; RuO 2; Sb 2o 3; SnF 2; SnO 2; SrO 2; TiS 2; TiF 3; V 2o 3; V 2o 5; VF 3; WS 2; ZnF 2; And combination.
Transition material can be by carrying out the cation electric discharge of exothermic reaction with transition material.Cation normally cheaply with lightweight (less atomic weight).Particular instance comprises Mg, Na and Li.As an example, for FeF 3transition material and Li cation, when producing or under discharge condition time, transition material can be to be similar to Li 3feF 3the amorphous mixture of lithium, iron and fluorine of ratio.In some embodiments, three kinds of elements mix up hill and dale on atomic size.In multiple embodiments, the iron that is characterized as about 1:1.5:1.5 to 1:4.5:4.5 of transition material: fluorine: the ratio of lithium.
Some disclosed embodiment relates to the purposes of lithium ion and the redox reaction as the metal fluoride of energy source in cathode material.As an example, under charged state, suitable cathode material is very short grained ferric flouride, and it can be (for example about 5nm on minimum cross section) or glassy state or the amorphous state of quantum dot size.In some embodiments, the electrode that metal fluoride redox material is made is for having the battery of for example inorganic electrolyte of solid electrolyte.This electrolytical instantiation is LiPON.
In some embodiments, the electric discharge of negative electrode is accompanied by reacting of ferric flouride or other transition metal fluorides and lithium ion, described lithium ion migrate into or insert ferric flouride matrix and there reaction form lithium fluoride and fe.The large Gibbs free energy relevant with this reaction provides very high utilisable energy for battery.This energy can insert with the standard lithium that uses in traditional lithium ion battery (or the lithium that depends on electrode matrix embeds) cathode material, and such as the energy of lithium and cobalt oxides, lithium manganese oxide, lithium titanate etc. is compared.Material disclosed herein in discharge process each transition metal in conjunction with a large amount of lithium atoms.In charging process, insertion reaction relate to each transition metal at the most lithium atom (for example, when lithium is from Li +revert to Li 0time, cobalt is from Co 3+be oxidized to Co 4+), and in conversion reaction, for example, generate FeF 3those reaction in, each transition metal reacts with three lithium atoms.In fact, be drawn out of electrode structure and become unstable because if exceed 1/2 lithium, insert the each transition metal of compound so most of and react lithium atom half.This is that transition metal electrode material disclosed herein for example provides, than traditional electrode material (LiCoO 2140mAh/g) the obvious reason of higher capacity (for example 700mAh/g or larger).In the time that electrode has suitable high ion disclosed herein and electron conduction, even under high speed and repeatedly, after circulation, still can obtain this capacity.
The challenge relevant with this technology is the slow mass transfer that lithium ion passes the fluoride of iron or the fluoride matrix of lithium (it can be particle form).As a result because in many application in required time period of battery charge or discharge many reaction site be unapproachable, so do not realize all told of material.In addition, because lithium ion is oversize through diffusion and the transit time of matrix, so the rate capability of material is relatively poor.Further, significantly mass transfer overpotential is accompanied by the charging and discharging to these materials.This overpotential cause being delivered to answer use lower energy, can cause the more heat of problem in system level to generate and increase the lower efficiency of user cost.This challenge also may reside in the battery of the transition material that adopts metallics, the oxidizing substance of non-fluoridate and/or the reductive cation material of non-lithium ion with non-iron, as mentioned above.
In order to tackle the challenge of slow mass transfer, the cathode material that contains elemental metals or alloy and lithium compound (under discharge condition) or metallic compound (under charged state) can provide with the form on very little particle or nanometer farmland.In some embodiments, these particles or farmland have about 20nm or less, or about 10nm or less intermediate value characteristic size.In some respects, particle or farmland have about 5nm or less intermediate value characteristic size.In some cases, transition material can be glassy state or unbodied material.In some embodiments, the particle of negative electrode or farmland have very closely and to distribute, and for example about 50% or less standard deviation.In some embodiments, in electrode, particle or the farmland at least about 90% has about 1 to 5nm characteristic size.In some embodiments, particle characteristic size has about 20nm or less or about 10nm or less or about 5nm or less d 50value.D 50be defined as 50% particle than its little characteristic size.Particle or the farmland arbitrfary point in the operating period of negative electrode can exist with these sizes.In some instances, particle or farmland exist with these sizes in the negative electrode of manufacturing.In some instances, after the complete charge/discharge cycle for the first time after the electric discharge for the first time of negative electrode or at negative electrode of particle or farmland, exist with these sizes.In some embodiments, the characteristic size of the particle of negative electrode or the average-size on farmland for example, changes and is no more than about 500% or about 100% after repeatedly circulation (, 10 circulations, 50 circulations, 100 circulations or 500 circulations).
Very little composition separation distance described herein provides the shorter the evolving path that moves to reactive metal compound site (electric discharge) in particle/farmland from the outside on particle or farmland or move to surface, particle/farmland (charging) from the lithium compound in particle/farmland for lithium or other electropositivity ions.For example, in charging process, lithium ion must depart from lithium fluoride, and is transferred to the outside on particle/farmland, there lithium ion contact electrolyte.Depart from behind particle/farmland some other ionic conduction matrixes that lithium ion may be had in contact electrode before arrival electrolyte.On the contrary, in discharge process, lithium ion is through entering the path in electrode body from electrolyte, and in described electrode body, lithium ion is arriving the segment distance of must advancing before target particles/farmland, and it enters and penetrate described particle/farmland and then finds reactive metal compound site.Only, after this multistage transmission, lithium ion just participates in redox reaction to produce electrochemical energy (electric discharge).In charging process, reverse path is contrary.Negative electrode can be moved with improved rate capability with little active material separation distance, this is unavailable before.
The other benefit that is derived from very little composition separation distance is relative shorter diffusion length between metallic atom and anion.Due to metal and anion atoms larger and heavier, their transmission is generally slower than lithium.The nanostructure providing is placed on metallic atom in the place that approaches very much anion, has reduced its distance that must spread.
The other challenge that realizes the potential benefit of transition material is derived from the high surface/mass ratio of very little particle.Large surface area (as the function of the quality of reactive explosive) causes the active material of major part to be converted to solid electrolyte interface (SEI) layer, and it extracts many available lithiums out also makes it exist with unsettled form.Therefore, due to can continued growth for several circulation SEI layers, so it also causes shorter cycle life.In cyclic process, experience the SEI forming around the particle of obvious change in volume and sometimes may break, the unsalted surface that must be covered by SEI is provided.The energy that the SEI of growth contains storing in battery does not have contributive material, and may form barrier to lithium transmission, reduces the rate capability of battery.
In some embodiments, this second challenge is by being used solid electrolyte to deal with.Solid electrolyte provides ionic conduction medium in the formation of SEI layer, and does not consume the active material of obvious amount.Therefore, cathode material can keep its high reversible capacity inherently.But should be understood that in other embodiments, negative electrode as herein described uses together with gel phase electrolyte with liquid.
Can use and be permitted eurypalynous solid electrolyte layer.In some cases, electrolyte has higher lithium ion conductive, and for example at least about 10 -6siemens/cm or at least about 10 -3siemens/cm.Can comprise LiPON and similar lithium ion conductor as the example of the inorganic material of unique dielectric substrate.
Figure 1A illustrates a kind of form of solid-state energy storage device as herein described.Device (100) comprise isolated anode (140) and negative electrode (150) and be placed in anode and negative electrode between solid electrolyte (130).
Figure 1B illustrates to have the anode current collector in abutting connection with anode (110) and a kind of form in abutting connection with the solid-state energy storage device of the cathode current collector (120) of negative electrode.Usually, collector body is and the solid conduction matrix of the electrochemical active material close contact of electrode.The form of collector body comprises sheet material, foil, foams, net, perforated sheet etc.Collector body should be made up of the electric conducting material compatible with cathode material electrochemistry.Example comprises copper, aluminium, nickel, tungsten, titanium, tantalum, molybdenum, tantalum nitride and titanium nitride, steel, stainless steel and its alloy or mixture.
As used herein, solid-state energy storage device represents the energy storage device that comprises solid-state anode, solid state cathode, solid electrolyte and other optional features, but does not comprise any as anode, negative electrode or electrolytical non-solid component.
Electrode capacity
In some embodiments, as the negative electrode transition material of manufacturing has the specified vol that is full of electric cathode material at least about 600mAhr/g.In some embodiments, cathode material keeps this to be full of electric capacity after repeatedly circulating.Being full of electric material is stoichiometric metallic compound MX.The example of such compound comprises above-mentioned sulfide, fluoride, phosphide, selenides, nitride, oxide, chalcogenide, oxysulfide, oxygen fluoride, sulphur-fluoride, sulphur-oxygen fluoride and chloride.
In some embodiments, when negative electrode transition material can be after circulation repeatedly high rate discharge, keep this high power capacity.For example, in the time that the speed to be full of electric cathode material at least about 200mA/g is discharged, cathode material can keep the capacity at least about 600mAh/g.In some embodiments, described material keeps this capacity under the higher discharge rate that is full of electric cathode material at least about 600mA/g.In some embodiments, described material keeps this capacity under the discharge rate that is full of electric cathode material up to about 6000mA/g.This discharge rate can remain steady state value, or in discharge process, can change but not drop to below 200mA/g.In some embodiments, cathode material keeps high capacity (for example 600mAh/g in the time of 200mA/g) after charging subsequently in the time of high speed.In some cases, electrode material can keep so two-forty capacity 10 times or more times circulation.Conventionally it can keep this two-forty capacity even more of a specified duration, for example about 20 times or more times circulation or about 50 times or more times circulation or about 100 times or more times circulation or about 500 times or more times circulation.In each circulation, cathode material is emitted whole 600mAh/g electric charges.Can so circulate the voltage that makes negative electrode with respect to Li/Li +4V between 1V.In some embodiments, charge rate can be higher than 200mA/g, higher than 600mA/g or higher than 6000mA/g, and described material keeps the approximately at least capacity of 600mAh/g.
When the temperature range certain, for example, from about 0 degree Celsius to 100 degrees Celsius or from about 20 degrees Celsius to 100 degrees Celsius circulation times, can obtain high power capacity performance.
In a scheme, when about 100 degrees Celsius of charge/discharge rates with 200mA/g with respect to lithium an-ode 1 to 4V between circulation time, transition material provides the capacity that is greater than about 350mAh/g active material.In other schemes, electrode material provides the capacity that is greater than about 500mAh/g, or be greater than the capacity of about 600mAh/g, or be greater than the capacity of about 700mAh/g, in each case, capability value be for about 100 degrees Celsius with the charge/discharge rates circulation time of 200mA/g, with respect to lithium an-ode 1 to 4V between voltage range in the active material that circulates.In another program, when about 100 degrees Celsius of charge/discharge rates with 200mA/g with respect to lithium an-ode 1 to 4V between circulation time, electrode material as herein described provides the capacity of about 350mAh/g to 750mAh/g.In another program, when at the temperature of the speed at 400mA/g and 120 ℃ with respect to standard metal lithium electrode (Li/Li +) 1 to 4.5V between, or be greater than at the speed of 1C and more than 50 ℃ temperature with respect to Li 1.5 to 4V between while discharging, electrode material can have the specific capacity that is greater than about 400mAh/g.
In some cases, in the time discharging under these conditions, there is the high average discharge volt that is greater than about 2V by the negative electrode of such material manufacturing.For example, even if high performance cathodes material disclosed herein also keeps its good performance (height ratio capacity, high-energy-density, high average discharge volt and low hysteresis) in the time of high rate discharge.
In another program, the device that adopts cathode material as herein described about 100 degrees Celsius of charge/discharge rates with 200mA/g with respect to metal lithium electrode 1 to 4V between voltage range in provide the average voltage that is less than 1V to lag behind.In another program, when about 100 degrees Celsius of charge/discharge rates with 200mA/g with respect to metal lithium electrode 1 to 4V between circulation time, such device provide be less than 0.7V average voltage lag behind.In one embodiment, when about 100 degrees Celsius of charge/discharge rates with 600mA/g with respect to metal lithium electrode 1 to 4V between circulation time, described device provide be less than about 1V average voltage lag behind.In one embodiment, when about 50 degrees Celsius of charge/discharge rates with 200mA/g with respect to metal lithium electrode 1.5 to 4V between circulation time, described device provide be less than about 1V average voltage lag behind.This hysteresis level can keep at least 10 circulations or at least 30 circulations or at least 50 circulations or at least 100 circulations.
Voltage delay is poor between discharge voltage and charging voltage, and the two is all along with charged state changes.The poor efficiency (being lost in hot energy) that it represents battery, is caused by the stickiness of ion transfer or reaction conventionally.Therefore, need ultra-voltage to drive reaction, this guiding discharge voltage is lower than open circuit voltage, and charging voltage is higher than open circuit voltage.Low hysteresis represents that battery is efficient.
In the following discussion, multiple negative electrode composition is described.In each in these compositions, the shape and size on particle/farmland can change as discussed.As an example, in negative electrode, the particle/farmland of active material has about 20nm or less or about 10nm or less or about 5nm or less intermediate value characteristic size.In some embodiments, described material is glassy state or unbodied.In some embodiments, the particle/farmland of material has about 50% or less standard deviation.In some embodiments, the characteristic size on particle/farmland has about 20nm or less or about 10nm or less or about 5nm or less d 50value.
Cathode activity component-metal component and lithium compound component
In a scheme of aforementioned means, when described device is during in discharge condition, negative electrode comprises active component (transition material), the metal or alloy component that described active component comprises simple substance form and lithium compound component.
Usually, metal component can be mixture or the alloy of any metal or metal.In a scheme, metal component is mixture or the alloy of transition metal or transition metal.In a scheme, metal component is selected from mixture or the alloy of Bi, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W and Ru or aforementioned metal.In a scheme, metal component is selected from Fe, Cu, Mn and Co.In a scheme, metal component is Fe.In a scheme, metal component is Cu.In a scheme, metal component is Co.In a scheme, metal component is the alloy of iron and for example Co of another metal or Mn.
In a scheme, metal component comprises the first metal and bimetallic mixture or alloy.In a scheme of hybrid metal component, metal component comprises the first metal and bimetallic nanometer farmland separately.In another program, the nanometer farmland of the mixture that metal component comprises the first and second metals or alloy.In a scheme, the first metal is Fe, and the second metal is Cu.Usually, lithium compound component is any lithium compound that (i) moves to the lithium ion of anode and (ii) react the anion that components of metal compounds is provided with metal component that produces in the time of device charging.Therefore,, under charged state, cathode material comprises components of metal compounds.Anion in lithium compound can be generally any anion that forms lithium compound and form metallic compound under discharge condition under charged state.In a scheme, lithium compound is lithium halide, lithia, lithium sulfide, lithium nitride, phosphatization lithium, sulphur-lithium halide, lithium hydride or its mixture.In a scheme, lithium compound is lithium halide.In a scheme, lithium compound is the fluoride of lithium.
In a scheme, " conversion reaction " can be write:
aM + b Li c X ↔ M a X b + ( b * c ) Li + + ( b * c ) e - ↔ M a X b + ( b * c ) Li - - - ( 1 )
The left-hand side of equation 1 is illustrated in the active material of cathode of discharge condition, and wherein active material of cathode comprises metal component M and lithium compound component Li nx.C is the form oxidation state of anion X.
The right-hand side of equation 1 is illustrated in the system of charged state, and wherein active material of cathode has converted components of metal compounds M to ax b, and provide Li ion arrive anode and provide electronics to external circuit for diffusing through electrolyte.
X forms respectively stable compound Li with lithium and metal M nx and M ax bany anionic species.M can be generally any metal.In a scheme, M is transition metal.In a scheme, M is selected from Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W and Ru.In a scheme, M is selected from Fe, Co and Cu.In a scheme, M is Cu.In a scheme, M is Fe.In a scheme, M is Co.
Operable metallic compound M ax binstantiation include, but are not limited to following compound:
Figure BDA00003529726000171
In some embodiments, material described herein provides with particulate form (the unconnected particle that contains a series of dispersions).In some embodiments, described material provides with the form of one or more pantostrat, and described one or more pantostrat has for example lithium compound of matrix or the ion conductor that embed the nanometer farmland or the region that have metal component and/or lithium compound component.In some embodiments, the mixture that individual particle contains metal component and lithium compound component.In some embodiments, some particles only contain metal component.In some embodiments, some particles only contain lithium compound component.
Fig. 2 A represents four examples of electrode form.This figure is only an example, and it should not limit the scope of claim unreasonably.Those of ordinary skills can confirm many schemes, substitute and revise.Should be appreciated that above-mentioned particle or farmland are nanostructure (for example spaced to be less than the length dimension of about 20nm), and these particles or farmland can combine to form shown in example 1-4 once with second particle structure.
The upper left of example 1(Fig. 2 A) show an embodiment, the non-encapsulated nanometer farmland that wherein electrode active material comprises lithium fluoride, elemental metals and metal fluoride.Such material can exist with any charged state, but the most typically exists to discharge completely or to approach the state discharging completely.Example 2(upper right) show a kind of electrode form, wherein metal fluoride nano particle and lithium fluoride nano particle are encapsulated in simple substance matrix.Seal in example at each, seal unit and can be used as independently particle or exist as pantostrat.Example 3(lower-left) illustrate a kind of form, wherein metal fluoride matrix is sealed lithium fluoride nanometer farmland and elemental metals nanometer farmland.Example 4(bottom right) show a kind of form, wherein lithium fluoride encapsulated metal fluoride particles or nanometer farmland and elemental metals particle or nanometer farmland.
Fig. 2 B represents the particle that can use in ferric flouride and relevant transition material and the other example of nanometer domain structure.In the example of Fig. 2 B, the structure of upper left side is primary particle 211, and it can find in electric discharge negative electrode.The nanometer farmland of the dispersion that primary particle 211 comprises ferrous metal 213 and lithium fluoride 215.Conventionally, the characteristic lateral section of primary particle is of a size of about 100nm or less.As mentioned, the cross sectional dimensions on the nanometer farmland of composition primary particle is about 20nm or less (for example about 5nm or less).In some cases, nanometer farmland is that composition is uniform.
The second particle 217(not drawn on scale of the ferric flouride transition material of the representation of upper right electric discharge in Fig. 2 B).Second particle by primary particle 211 for example in the structure of upper left represented those and possible ion conductive material and/or the particle of electronic conductive material 219 form.Second particle can be aggregate or the agglomerate of the particle of primary particle and optional ion/electronic conductive material.In some embodiments, second particle exists with the form of slurry, for cover collector body in the time forming negative electrode.In some embodiments, the cross sectional dimensions of second particle is about 0.1 to 5 micron.The all sizes that occur in the discussion of Fig. 2 B are all intermediate values.
The lower-left presenting in Fig. 2 B and the structure of bottom right represent to be respectively full of primary particle 221 and the second particle 223 of electric ferric flouride transition material.Ferric flouride in the structure that other transition materials can alternate figures 2B represent and its discharging product.
The relative quantity of lithium compound component and metal component can change on a large scale, but should be applicable to battery unit.In other words, described component should not have the relative quantity of contributing or not strengthening the untapped material of conductivity to provide not introduce a large amount of conversions to electrochemical energy.In some embodiments, adopt iron as metal component, in active material of cathode, the mol ratio of iron and lithium is about 2 to 8, or about 3 to 8.In some embodiments, adopt divalent metal, for example copper, in active material of cathode, the mol ratio of metal and lithium is about 1 to 5.In multiple embodiments, cathode material is characterised in that about 1:3:3 or the iron from about 1:1.5:1.5 to 1:4.5:4.5: fluorine: the ratio of lithium.
Although should be appreciated that Fig. 2 A and 2B diagram LiF and metal-F material, the material of other types is also possible as explained above.For example, lithium fluoride can be by the combination replacement of lithium fluoride and lithium sulfide.In such example, metal fluoride can be by the combination replacement of metal fluoride/sulfide.
Cathode activity component-lithium metal compounds component
In another program of device, at some point of electrode charge state, negative electrode comprises the active component that contains lithium metal compounds component.Usually, lithium metal compounds component be comprise lithium, non-lithium metal and anion and in the time of the charging of described device, produce and move to the lithium ion of anode and any compound of metallic compound.
In a scheme, such reaction can be write:
Li d M e X f ↔ dLi + + de - + M e X f ↔ dLi + M e X f - - - ( 2 )
The left-hand side of equation 2 is illustrated in the active material of cathode of discharge condition, and wherein cathode activity component comprises lithium metal component Li dm ex f, the right-hand side of equation 2 is illustrated in the system of charged state, and wherein active material of cathode has converted components of metal compounds M to ex f, and provide lithium ion arrive anode and provide electronics to external circuit for diffusing through electrolyte.In reaction 2, the whole lithiums in lithium metal compounds all convert lithium ion to.In another program, in lithium metal compounds, be less than whole lithiums and convert lithium ion to.A scheme of such reaction provides in equation 3
Li d M e X f ↔ g Li + + ge - + Li d - g M e X f - - - ( 3 )
Wherein g<d.According to Li d-gm ex fthe thermodynamics and kinetics stability of compound, such compound can be used as Li d-gm ex fexist, maybe can be disproportionated into the mixture of one or more of lithium compounds, metallic compound and lithium metal compounds.
In a scheme, lithium metal compounds component is lithium metal oxide, lithium metal sulfide, metal lithium nitride, lithium metal phosphide, lithium metal halide or lithium metal hydride or its mixture.In a scheme, lithium metal compounds component is lithium metal halide.In a scheme, lithium metal compounds component is lithium metal fluoride.In a scheme, lithium metal compounds component is lithium ferri-fluoride.In a scheme, lithium metal compounds component is lithium copper fluoride.In a scheme, lithium metal compounds component is lithium cobalt fluoride.
Cathode activity component-metal component, lithium compound component and lithium metal compounds component
In another program of device, at some points of electrode charge state, negative electrode comprises the active component that contains metal component, lithium compound component and lithium metal compounds component.Metal component, lithium compound component and lithium metal compounds component can be as above.In the scheme of device, metal, lithium, metallic compound and/or lithium compound can have 30nm or less or 20nm or less or 10nm or less or 5nm or less intermediate value characteristic size.In some cases, described component is mixed with individual particle or layer, and separates with pointed length dimension each other and/or exist together with glassy state or amorphous state in these particles or layer.
Cathode activity component-components of metal compounds
As found out from above equation 1,2 and 3, under charged state, cathode activity component comprises the components of metal compounds that contains metal and anion.In a scheme, components of metal compounds is oxide, nitride, sulfide, phosphide, halide, sulphur-halide or the hydride that is selected from the metal of Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W and Ru.In a scheme, components of metal compounds is the fluoride that is selected from the metal of Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W and Ru.In a scheme, components of metal compounds is the fluoride that is selected from the metal of Fe, Cu or Co.In a scheme, components of metal compounds is FeF 3, FeF 2, CuF 2, CoF 2or CoF 3.In a scheme, components of metal compounds is FeF x, wherein x is 1 to 3.In a scheme, components of metal compounds is CuF x, wherein x is 1 to 3.In a scheme, components of metal compounds is CoF x, wherein x is 1 to 3.
Negative electrode MEIC, electronic conductor and ion conductor
In a scheme of device, negative electrode comprises the mixed electronic-ionic conduction component (" MEIC component ") together with above-mentioned active component.MEIC component generally can be by compatible with the other materials of device and allow to be enough to make the electronics of device operation and any material of lithium ion transmission to make.In a scheme, MEIC component is to have 10 under device operating temperature -7the material of S/cm or larger electronic conductivity.In a scheme, MEIC component is to have 10 under device operating temperature -7the material of S/cm or larger lithium ion conductivity.Can include but not limited to as the example of the material of MEIC component the titanate of lithium, the phosphate of lithium iron, the oxide of vanadium, the oxide of cobalt, the oxide of manganese, the sulfide of lithium, the sulfide of molybdenum, the sulfide of iron, LiPON, MoO 3, V 2o 5, carbon, the oxide of copper, lithium inserts such as LiCoO of compound 2, Li (CoMn) O 2, LiMn 2o 4, Li (CoNiMn) O 2, Li (NiCoAl) O 2or there is the other materials of higher lithium ion conductivity.In a scheme, MEIC component is made up of the material identical with solid electrolyte.In a scheme, MEIC component is made up of the material different from solid electrolyte.MEIC component itself can have electro-chemical activity (for example MoO 3or V 2o 5) or can not show electro-chemical activity (for example LiPON).In a scheme, MEIC is LiPON.
If negative electrode comprises MEIC component, the minimum of MEIC component can be generally to allow to be enough to make the lithium ion of device operation and the amount of electric transmission so.Maximum is when the amount that the specific capacity of needs or the MEIC of other electrical features are provided for the cathode material of electro-chemical activity in the time that speed, voltage range and the charged state of needs are moved.In a scheme of the device that comprises MEIC, the minimum of MEIC is about 1% by the weighing scale of cathode material.In a scheme of the device that comprises MEIC, the minimum of MEIC is about 5% by the weighing scale of cathode material.In a scheme of the device that comprises MEIC, the maximum of MEIC is about 50% by the weighing scale of cathode material.In a scheme of the device that comprises MEIC, the maximum of MEIC is about 25% by the weighing scale of cathode material.
MEIC material can provide in a variety of forms in electrode.In an example, the granule of MEIC mixes and compresses with electro-chemical activity particle.In another example, MEIC covers active material particle.In a further example, MEIC is arranged in vertical line.MEIC can be made up of bi-material at least, and a kind of have a high electron conduction, and another kind has high ionic conductivity.
In some schemes of described device, the electronic conductor that negative electrode comprises dispersion is to increase the electron conduction of electrode.In multiple schemes, this component has higher than 10 -7the electron conduction of S/cm.In some embodiments, this compound can be carbon or metallic compound.The example of the form of the carbon that can adopt comprises graphite, active carbon, nanotube, nanofiber, nano wire, Graphene, graphene oxide etc.In the time existing, electronic conductor can be with about 20 % by weight of active material in negative electrode or lower, or about 10 % by weight or lower amount exist.For example, this material can be provided as nano wire, nano particle, nanocrystal, and can be orientated to electrolytical direction along electrode, or can be random dispersion.In some embodiments, described material forms the percolating network that spreads all over negative electrode.
In some schemes of described device, the Li that negative electrode comprises dispersion +ion conductor is to increase the ionic conductivity of electrode.For example, this material can provide with the form of nano wire, nano particle, nanocrystal, and can be orientated to electrolytical direction along electrode, or can be random dispersion.Ionic material can form with the coating around active material particle.In some embodiments, described material forms the percolating network that spreads all over negative electrode.In some scheme, described material has at least 10 under the operating temperature of device -7the ionic conductivity of S/cm.In some cases, described material has at least 10 -5the ionic conductivity of S/cm, or described material has and is greater than 10 -4the ionic conductivity of S/cm.There is this Li +the material of conductivity is known in this area; Non-limiting list comprises LiFePO4, carbon, Li 2o-SiO 2-ZrO 2, Li-Al-Ti-P-O-N, LiMO 2, Li 10geP 2s 12, Li 1.5al 0.5ge 1.5(PO 4) 3, Li 7la 3zr 2o 12, Li 9siAlO 8, Li 3nd 3te 2o 12, Li 5la 3m 2o 12(M=Nb, Ta), Li 5+xm xla 3-xta 2o 12sulfide, lithium phosphate, Lisicon, sulfo--lisicon, glassy structure, lanthanium titanate lithium, garnet structure, β ' ' aluminium oxide and the lithium solid electrolyte of the sulfide of (M=Ca, Sr, Ba), LiPON, lithium, lithium ferrum sulfide, iron.In scheme, the ionic conductivity of described material is at least greater than electrolytical ionic conductivity.Ion conductor is preferably with about 20 percentage by weights of active material in negative electrode or lower or more preferably about 10 percentage by weights or lower amount exist.
Negative electrode pattern
In a scheme of described device, negative electrode is the film that comprises active component and optional MEIC component.Can use any above-mentioned active component and MEIC component.Film can be pantostrat, the sedimentary deposit of for example sputter.Or film can be the layer that comprises particle and/or nanometer farmland, and optionally keeps together by binding agent.In a scheme, the thickness of film cathode is about 2.5 to 500nm.In another program, the thickness of film cathode is between about 5 to 300nm.In another program, the thickness of film cathode is about 200nm or larger.In some cases, the component of cathode material (transition material) is mixed mutually with individual particle or layer, and separates with the length dimension above indicating each other and/or exist together with glassy state or amorphous state in these particles or layer.In some cases, described component provides with nanometer farmland.
Negative electrode pattern-metal compound particles/nanometer farmland
For the device that wherein comprises components of metal compounds and optional MEIC, in a scheme, particle/nanometer farmland that negative electrode comprises optional MEIC and components of metal compounds.The particle that contains components of metal compounds or nanometer farmland can be generally arbitrary shape and size.In a scheme, the particle that at least some contain metal component or nanometer farmland are close to spherical.But they can be also other shapes, for example the combination of bar-shaped, wire, pillow, polygon, sheet and any these shapes, comprises or does not comprise spherical.As used herein, " close to spherical " represents that three linear dimensions of particle do not have the characteristic length of the characteristic length twice that exceedes one of other two sizes.Should understand can be substituted by aspheric particle or nanometer farmland close to spherical particle or nanometer farmland hereinafter described.In this class situation, said " diameter " can regard the characteristic size of particle as, and this characteristic size is the shortest path across particle or nanometer farmland.
In a scheme, the particle that at least some contain components of metal compounds or nanometer farmland are close to spherical, and such particle has the median diameter between about 1 to 20nm.In a scheme, the particle that at least some contain components of metal compounds or nanometer farmland be close to spherical, and such particle or nanometer farmland have between about 3 to 10nm, or median diameter between about 1 to 5nm.The diameter on particle or nanometer farmland can be measured by method known to those skilled in the art; Method comprises visual examination, dynamic light scattering, laser diffraction of SEM and TEM microphoto etc.In a scheme, the particle of the fluoride that components of metal compounds comprises iron or nanometer farmland.In a scheme; particle or the nanometer farmland of the fluoride (ferric flouride and/or ferrous fluoride) that components of metal compounds comprises iron, fluoride, the fluoride of cobalt or the fluoride of manganese of copper; wherein at least some are close to spherical, and such spheric granules or nanometer farmland have the median diameter between about 1 to 20nm.In a scheme; the particle of the fluoride that components of metal compounds comprises iron, the fluoride of copper, the fluoride of cobalt or the fluoride of manganese or nanometer farmland; wherein at least some are close to spherical, and such spheric granules or nanometer farmland have at the median diameter between about 3 to 10nm or between about 1 to 5nm.In some cases, the component of cathode material (transition material) is mixed with individual particle as herein described, and in these particles, they separate with the length dimension above indicating each other and/or exist together with glassy state or amorphous state.
In a scheme, negative electrode comprises MEIC component and embeds the particle of the components of metal compounds of the matrix of MEIC component.The particle of components of metal compounds or nanometer farmland can be as described above.
Negative electrode pattern-metallic particles/nanometer farmland and lithium compound particle/nanometer farmland
For the device that wherein active material of cathode comprises metal component, lithium compound component and optional MEIC under some charged states; in a scheme, the particle of the particle that negative electrode comprises optional MEIC and metal component or nanometer farmland and lithium compound component or nanometer farmland.The particle of the particle of metal component and lithium compound component can be generally any shape and size.Such active material can comprise some particles that only contain metal or nanometer farmland and the other particle that only contains lithium compound or nanometer farmland (rather than not only contain metal but also contain lithium compound particle).In other embodiments, some or all particles not only contain metal but also contain lithium compound.Herein unless otherwise indicated, particle can be (for example, not only the containing metal but also contain lithium compound in particle) of homogeneous phase (only containing metal, lithium compound or other materials) or the out-phase that contains two or more materials in individual particle.In the time that they are out-phase, the component of cathode material (transition material) is mixed in individual particle, and in these particles, they separate with the length dimension above indicating each other and/or exist together with glassy state or amorphous state.
In a scheme, the particle of at least some metal components or nanometer farmland are close to spherical.In a scheme, the particle of at least some metal components or nanometer farmland be close to spherical, and such particle or nanometer farmland have 1 to 20nm median diameter.In a scheme, the particle of at least some metal components or nanometer farmland be close to spherical, and such particle or nanometer farmland have about 3 to 10nm median diameter.In a scheme, the particle that metal component comprises iron, copper, cobalt or manganese or nanometer farmland.In a scheme, the particle that metal component comprises iron, copper, cobalt or manganese or nanometer farmland, wherein at least some are close to spherical, and such spheric granules or nanometer farmland have about 1 to 20nm or about 3 to 10nm or about 1 to 5nm median diameter.
Negative electrode pattern-lithium metal compounds particle or nanometer farmland
For the device that wherein negative electrode comprises lithium metal compounds component and optional MEIC under some charged states, in a scheme, the particle that electrode comprises optional MEIC and lithium metal compounds component or nanometer farmland.The particle of lithium metal compounds component or nanometer farmland can be generally arbitrary shape and size, comprise those for other components mentioned above.
Solid electrolyte
Solid electrolyte generally can be by making with the compatible any material of other materials of device, and it has the enough large lithium ion conductives that are allowed for that the lithium ion of device operation passes through, and has the enough little electron conduction for installing operation.In a scheme, solid electrolyte has and is greater than 10 under 100 degrees Celsius -7the lithium ion conductive of S/cm.Preferably, under 100 degrees Celsius, described material has at least 10 -5the ionic conductivity of S/cm, even more preferably, described material has and is greater than 10 -4the ionic conductivity of S/cm.In a scheme, solid electrolyte has and is less than 10 under 100 degrees Celsius -10the electronic conductivity of S/cm.In a scheme, solid electrolyte is selected from LiPON, lithium aluminium fluoride, Li 2o-SiO 2-ZrO 2, Li-Al-Ti-P-O-N, Li 3xla 2/3-xtiO 3, Li 10geP 2s 12, Li 1.5al 0.5ge 1.5(PO 4) 3, Li 7la 3zr 2o 12, Li 9siAlO 8, Li 3nd 3te 2o 12, Li 5la 3m 2o 12(M=Nb, Ta), Li 5+xm xla 3-xta 2o 12(M=Ca, Sr, Ba), LiPON, lithium phosphate, Lisicon, sulfo--LiSICON, Li 2s-X (X=SiS 2, GeS 2, P 2s 5, B 2s 3, As 2s 3), Li aal bga cb ds e(PO 4) f, Li aal bga cb ds e(BO 3) f, Li age bsi cs d(PO 4) e, Li age bsi cs d(BO 3) e, anti-perovskite hydrate, glassy structure, lanthanium titanate lithium, garnet structure, β ' ' aluminium oxide and other lithium solid electrolytes.In a scheme, solid electrolyte is LiPON.In a scheme, solid electrolyte is lithium aluminium fluoride.In a scheme, solid electrolyte is LiAlF 4.In some embodiments, use liquid or gel electrolyte and there is no solid electrolyte.Such electrolyte can be any type using together with traditional lithium ion battery.
Anode material
Negative pole generally can be made up of any material compatible with the other materials of device, in the time installing in charged state, can store lithium atom or ion, can be provided for being embedded into the lithium ion in negative electrode in the time installing in discharge condition.In a scheme of device, negative active core-shell material is lithium metal.In a scheme of device, negative material is high power capacity, the low voltage material of lithium silicide, Li-Sn or other and lithium alloyage.In a scheme of device, negative active core-shell material is to be embedded into for example lithium in graphite of carbon component.In some cases, negative active core-shell material is the material that can insert with the reversible capacity higher than carbon lithium ion.Such material comprises the oxide of tin, magnesium, germanium, silicon, these materials etc.
In a scheme of device, negative material is the porous material allowing in lithium plating hand-hole, thereby alleviates the bulbs of pressure, otherwise the bulbs of pressure can act on electrolyte by cathode expansion due to lithium plating.In a scheme, described hole is carbon nano-tube, carbon bucky-ball, carbon fiber, active carbon, graphite, porous silicon, aeroge, zeolite, xerogel etc.
In a scheme of device, form in the Anodic of the charging cycle for the first time original position of battery.If device is with the state manufacture (using the negative electrode of lithiumation) of electric discharge, charging cycle can be extracted lithium out and is deposited on anode-side from negative electrode for the first time.In the situation that anode is lithium anodes, therefore by plating in anode current collector, original position forms anode.In this case, preferably, anode current collector is the metal that does not form alloy or do not react with lithium with lithium; The non-limiting list that may select of anode current collector metal comprises TaN, TiN, Cu, Fe, stainless steel, steel, W, Ni, Mo or its alloy.In a scheme, in the device of manufacturing, there is excessive lithium at cathode side.In another program, in the device of manufacturing, in anode-side, may in anode current collector, there is excessive lithium.Excessive lithium is wished, to extend the cycle life of battery, because some lithiums can form alloy due to side reaction, with collector body or react and inevitably loss with the air and/or the water that are leaked into device.
In a scheme of device, exist and substantially prevent that sky G&W from entering sealing of active material.Described sealing can be LiPON, oxide, nitride, oxynitride, resin, epoxy resin, polymer, Parylene, metal (for example Ti or Al) or its multiple layer combination.Moisture and oxygen barrier are known in packaging for foodstuff, semiconductor packages etc.
Collector body
Device as herein described comprise optional just and/or negative electrode collector.Collector body generally can be by making by any material from external circuit conveying electronic to male or female or from male or female conveying electronic to external circuit.In a scheme, described device does not comprise cathode current collector, and electronics is directly transferred to negative electrode and transferred to external circuit from negative electrode.In a scheme, described device does not comprise anode current collector, and electronics is directly transferred to anode and transferred to external circuit from anode.In a scheme, described device neither comprises that cathode current collector does not comprise anode current collector yet.In a scheme, negative electrode collector is metal, for example copper.In a scheme, negative collector body is copper alloy.In a scheme, negative collector body is the alloy that copper and the metal that is selected from nickel, zinc and aluminium form, or covers the copper in metal or polymer foil.In a scheme, collector body is copper, and comprises the non-copper metal layer being placed between copper and negative electrode or anode material.In a scheme, positive collector body is metal, for example copper, and comprise the nickel, zinc or the aluminium lamination that are placed between copper and anode material.In a scheme, positive collector body is aluminium.In a scheme, positive collector body is aluminum or aluminum alloy.In a scheme, positive collector body is aluminium, and comprises the non-aluminum metal layer being placed between aluminium and negative electrode or anode material.In a scheme, collector body is steel or stainless steel.In a scheme, collector body is steel or stainless steel, and comprises the non-steel metal level being placed between steel and negative electrode or anode material.Cathode current collector and negative electrode collector can be to be selected to enumerate the different materials of material above or be same material on the contrary.
Energy density
In a scheme, when under 100 degrees Celsius with respect to Li 1 to 4V between circulation and when at least approximately the current rate of 200mAh/g active material of cathode is measured, device as herein described has the energy density of at least about 50Whr/kg or about 50 to 1000Whr/kg.In another program, device as herein described has about 100 to 750Whr/kg energy density.In another program, device as herein described has about 250 to 650Whr/kg energy density.In another program, device as herein described has the energy density that is greater than about 250Whr/kg.As used herein, energy density is the energy density in device level; Be stored in gross energy in the device quality divided by device, wherein the quality of device comprises the quality of the packing of anode, negative electrode, electrolyte, collector body and device.From the viewpoint of volume, in some embodiments, under condition mentioned above, described device has at least approximately energy density of 600Wh/L.
In a scheme, in the time measuring at the temperature of 100 degree, negative electrode as herein described has about 500 to 2500Whr/kg electrode energy density.In another program, negative electrode as herein described has about 800 to 1750Whr/kg electrode energy density.In another program, negative electrode as herein described has about 1000 to 1600Whr/kg energy density.In another program, negative electrode as herein described has the energy density that is greater than about 1000Whr/kg.As used herein, electrode energy density is the energy density in electrode level; Be stored in gross energy in the device quality divided by negative electrode under discharge condition, wherein the quality of electrode comprises the quality of any electrochemistry inactive ingredients (for example ion or electronic conductor additive) in electrochemical active material, lithium, positive collector body and negative electrode.
Mixed fluoride thing/sulfide negative electrode
In a scheme, in some points of charged state, the lithium compound component that negative electrode comprises metal component and contains lithium, fluorine and sulphur.In a scheme, the mixture that lithium compound component contains lithium fluoride and lithium sulfide.In a scheme, the sulphur fluoride that lithium compound component contains lithium.In a scheme, the metal component of the alloy that negative electrode contains lithium, fluorine, sulphur and chosen from Fe, copper, cobalt, manganese, bismuth or these metals.In a scheme, negative electrode contains the compound that comprises lithium, fluorine, sulphur and iron.In a scheme, the metal component of the alloy that negative electrode contains lithium fluoride, lithium sulfide and chosen from Fe, copper, cobalt, manganese, bismuth or any these metals.In a scheme, negative electrode contains lithium fluoride, lithium sulfide and iron.In a scheme, the lithium fluoride (3LiF+Fe can be the LiF of 58wt%) that negative electrode contains about 30 to 80 % by weight, lithium sulfide and the metal component of about 1 to 20 % by weight.In a scheme, negative electrode contains at the lithium sulfide of the lithium fluoride of about 40 to 70 % by weight, about 2 to 15 % by weight and the iron of about 30 to 60 % by weight.In a scheme, the lithium fluoride that negative electrode contains about 50 to 70 % by weight, the lithium sulfide of about 0 to 20 % by weight and about percent 20 iron to 50 % by weight.In a scheme, when electrochemical cell is during in relative discharge condition, negative electrode contains lithium fluoride, lithium sulfide and metal component, and when state in more charging, contains metal fluoride and lithium sulfide and optional lithium fluoride and metal component.In such scheme, negative electrode does not basically contain metal sulfide at the state of charging more.In a scheme, in the time of the state of electrochemical cell in relative electric discharge, negative electrode contains lithium fluoride, lithium sulfide and iron, and in the time of the state of more charging, the fluoride that contains iron and lithium sulfide and optional lithium fluoride and iron component.In such scheme, negative electrode does not basically contain metal sulfide under the state of charging more.In a scheme, in the time of the state of electrochemical cell in relatively electric discharge, negative electrode contains lithium fluoride, lithium sulfide and metal component, and in the time of the state of more charging, contains metal fluoride and metal sulfide and optional lithium fluoride, lithium sulfide and metal component.In a scheme, in the time of the state of electrochemical cell in relatively electric discharge, negative electrode contains lithium fluoride, lithium sulfide and iron, and in the time of the state of more charging, the fluoride that contains iron and the sulfide of iron and optional lithium fluoride, lithium sulfide and iron component.In other schemes, sulfide composition can be sulfide (FeS or the FeS of iron 2), the sulfate of iron, the sulfide of copper, lithium sulfide (Li xand/or solid sulfur S).Have been found that FeS, FeS 2and Li 2s is obviously than the oxide of other known conductive lithiums for example LiPON, MoO x, VO x, LiFePO 4with the better lithium ion conductor of lithium titanate.
In some embodiments, the battery that contains the negative electrode with sulfide or other conduction reinforcing agents circulates in the nonreactive scope of conduction reinforcing agent.The sulfide of known iron is converting fe and sulphur with respect to lithium/lithium-ion electric under to the voltage of about 1.7 volts.It is believed that elemental sulfur can damage some solid electrolyte (especially oxide type solid electrolyte), so may be desirably in the formation that prevents sulphur in normal circulation.In order to prevent that sulfide electrochemical reduction from generating sulphur, described device is by using battery management circuit or other controlling organizations to be configured to prevent that negative electrode from reaching 1.7 volts in discharge process.In a word, select " cut-off " voltage so that the electrochemical reaction of expecting occurs completely or approaches (in electrode, whole or most of electrochemical active materials change) completely, and conduction enhancing component is not reacted.In the case of the sulfide system of the sulfide-iron of iron, for example, be generally suitable to the discharge voltage of (about 2 volts) between about 1.8 to 2.2 volts with respect to lithium/lithium-ion electric.
In some embodiments, described device comprises the intermediate layer being placed between negative electrode and electrolyte.This intermediate layer can stop sulphur or other materials to move to electrolyte and damage electrolyte.Intermediate layer also should conductive lithium ion, and under negative electrode working voltage and stable with respect to cathode material and electrolyte,
In some embodiments, matrix or other strong binding agents are for keeping conducting reinforcing material and active material of cathode very approaching in the circulation repeating.Observed conducting reinforcing material (sulfide of for example iron) and active material of cathode in normal circulation along with passage of time can separate.If there is this phenomenon, electrode performance is undermined so.Conducting reinforcing material should approach (generally at nano-scale) in electrochemical active material very much.This very approaching relation can be established in manufacture process, then in cyclic process, keeps by use matrix.Matrix is ion and electronic conductor.The example of suitable basis material comprises LiF, AlF 3, LiAlF 4, SiO 2, Al 2o 3, MoO 3, MoS 2, LiFePO 4, VO xand LiTiO x.
In some scheme, basis material is provided as pantostrat, and described pantostrat embeds the particle separating or the nanometer farmland that have conduction reinforcing agent and active material.Two examples are referring to Fig. 3.For example, when negative electrode is during in discharge condition, matrix embeds the sulfide of (i) iron and (ii) particle separating or the nanometer farmland of fe and lithium fluoride.In another example, when negative electrode is during in discharge condition, matrix embeds the sulfide of (i) iron and (ii) fe and (iii) particle separating or the nanometer farmland of lithium fluoride.In some embodiments, conduction reinforcing agent provides with the layout of core-shell, has the active material (for example iron and/or lithium fluoride) that conduction reinforcing agent (sulfide of for example iron) covers.So core-shell particles can embed matrix mentioned above.In some scheme, matrix, active material and conduction reinforcing agent provide with same little particle.For example, basis material can be sealed two or more granules or nanometer farmland, and wherein at least one is active material, and wherein at least another kind is conduction reinforcing agent.In some embodiments, composite particles can have the intermediate value characteristic size of about 5nm to 100nm.
Negative electrode/electrolyte intermediate layer
In a scheme, the negative electrode under discharge condition contain metal component and be placed in negative electrode and electrolyte between intermediate layer, this intermediate layer is impermeable for metal component substantially.In some embodiments, intermediate layer is improved cycle performance by preventing migration and/or cathode material with electrolytical reaction.In a scheme, intermediate layer comprises one or more of following materials: lithium fluoride, silicon dioxide, aluminum phosphate, aluminum fluoride, aluminium oxide and molybdenum oxide.In a scheme, intermediate layer is lithium fluoride.In a scheme, intermediate layer is silicon dioxide.In a scheme, negative electrode contains iron, and intermediate layer is lithium fluoride.In a scheme, electrode contains iron, and intermediate layer is silicon dioxide.In a scheme, the thickness in intermediate layer is between about 2 to 50nm.In a scheme, negative electrode contains iron, and intermediate layer is the lithium fluoride of thickness between about 2 to 50nm.In a scheme, negative electrode contains iron, and intermediate layer is the silicon dioxide of thickness between about 2 to 50nm.In a scheme, electrolyte is LiPON, and negative electrode contains iron, and intermediate layer is lithium fluoride.In a scheme, negative electrode contains iron, and intermediate layer is silicon dioxide.In a scheme, negative electrode contains iron, and intermediate layer is the lithium fluoride of thickness between about 2 to 50nm.In a scheme, negative electrode contains iron, and intermediate layer is the silicon dioxide of thickness between about 2 to 50nm.
Excessive lithium in a small amount
Traditional lithium ion battery of manufacturing contains a large amount of excessive lithium that exceedes the complete charging and discharging requirement of battery conventionally.Particularly, solid-state and/or film lithium ion battery contains and exceedes discharge the completely a large amount of excessive lithium of requirement of battery.The volume with the negative pole of a large amount of excessive lithiums can not change to vast scale amount.For example, conventionally use 4 times of excessive lithiums.Be in operation, circulating battery is to the anode lithium of only having about 20%, and therefore change in volume is only 20%.
In a scheme of battery described herein, there is excessive in a small amount lithium.In a scheme, exist lower than the excessive lithium of 25 % by weight.While alleviation, only the excessive lithium of 25 % by weight will cause about 500% negative pole change in volume, and this will apply larger pressure to electrolyte.
A kind of mode of tackling this challenge is to control change in volume by changing electrode structure.In addition, glassy state electrolyte can bear the bending that in the negative pole on 100% order of magnitude, change in volume causes.In some embodiments, excessive lithium is plated in open pores (typically in negative pole), and this alleviates the expansive force on electrolyte.In various embodiments, no matter described hole is full of lithium or empty, and they all occupy identical volume.Can provide the example of the material in suitable hole to comprise nanotube (such as carbon nano-tube), carbon bucky-ball, carbon fiber, active carbon, graphite, porous silicon, aeroge, zeolite, xerogel etc.
The another way of tackling the volumetric expansion relevant with excessive lithium limited in battery relates to use and comprises the relatively more battery structure of " multiple pileup " of thin layer.Each stacking anode layer, dielectric substrate and cathode layer of comprising.In " one stacking " battery (traditional), all lithium is all in the anode that at least 50-200 μ m is thick, and the change in volume of anode can cause the expansion of the unaffordable 50-200 μ of battery m.But if battery contains the stacking of tens of (or hundreds of, or thousands of) in single battery, described in each, stacking thickness is for example nanometer more than 100, system coupling better between the expansion that is retracted to negative electrode of anode so.In some instances, the structure of multiple pileup can use for example anode/electrolyte/negative electrode of 100 layers, and every one deck is equivalent to 1/100 of conventional thickness.
In some embodiments, in battery, some or all excessive lithiums provide in made negative electrode.In some embodiments, cathode material has a certain amount of simple substance lithium and other components (for example metal and lithium compound particle or nanometer farmland) mentioned above.In some instances, lithium metal is with lower than about 50 % by weight or be present in active material of cathode lower than the level of about 30 % by weight.
For the application of device
Device described herein generally can be for needing any application of energy storage.The application that described device especially can be well suited for for example electric motor car, hybrid electric vehicle, consumer electronics device, medical electric device and electrical network storage and regulate.
Electrode manufacturing process
Negative electrode as herein described can be manufactured by many diverse ways.Be below to manufacture the list of option, comprise that material is synthetic and in the method for substrate overlying strata.
Vacuum technology, comprises sputter, evaporation, reactive evaporation, vapour deposition, CVD, PECVD, MOCVD, ALD, PEALD, MBE, IBAD and PLD.
Wet method is synthetic, comprises that CBD, plating, spraying and original position formation, Langmuir, Langmuir Blodgett, successively formation, electrostatic spray deposition, ullrasonic spraying deposition, aerosol spray pyrolysis, collosol and gel synthesize, one kettle way is synthetic and other methods from bottom to top.
Dry method is synthetic, comprise compacting, hot pressing, cold pressing, etc. synthetic, the plasma synthesis of static pressure, sintering, spark plasma sintering, flame pyrolysis, burning, atomization and melt spinning.
Method from top to bottom, for example jet grinding, wet method/dry grinding, lapping using star lapping machine and high energy milling.
Painting method, for example slit, spin coating, dip-coating, scraping blade, measuring stick (metering rod), groove casting (slot casting), silk screen printing, ink jet printing, aerosol injection, roll-type scraper, comma coating, anti-comma coating, flow casting molding, injection forming, concave surface coating and the coating of nick face.
Only for the synthetic method of material comprise that collosol and gel is synthetic, one kettle way synthetic, synthetic, melt spinning from bottom to top.The method only reducing for granularity comprises wet grinding, dry grinding, lapping using star lapping machine, high energy milling, jet grinding.Only comprise slit, spin coating, dip-coating, scraping blade, measuring stick, groove casting, silk screen printing, ink jet printing, aerosol injection, roll-type scraper, comma coating, anti-comma coating, flow casting molding, injection forming, concave surface coating, the coating of nick face for the method applying.The every other method of listing is some mixing of synthetic/deposition.
In some embodiments, cathode material uses sputter, PVD, ALD or CBD to produce.In a scheme, described device is manufactured by anode current collector, anode, electrolyte, negative electrode and cathode current collector sequential aggradation in substrate.In a scheme, there is no independent substrate, anode, electrolyte, negative electrode and cathode current collector Direct precipitation are in anode current collector.In a scheme, there is no independent substrate, negative electrode, electrolyte, anode and anode current collector Direct precipitation are in cathode current collector.
In some embodiments, the method that uses one or more of precursors wherein or reactant to contact in solid phase for the transition material of negative electrode is prepared.Can use many such methods.It is synthetic that they are collectively referred to as solid phase.Example comprises hot pressing, colds pressing, etc. synthetic, the plasma synthesis of static pressure, sintering, calcining, spark plasma sintering, flame pyrolysis, burning, atomization and melt spinning.Synthetic grinding and the mixing that relates to bulk precursor material of some solid phases.Massive material is ground to very little size, then combines or mix and react if desired to form the composition of expectation.Grinding can be undertaken by jet grinding, cryogrinding, lapping using star lapping machine (Netzsch, Fritsch), high energy milling (Spex) and other grinding techniques well known by persons skilled in the art.In some embodiments, the particle that calcining is ground and mixed.In some embodiments, lapping device is produced and is had about 20nm or more particle or the nanometer farmland of the intermediate value characteristic size of decimal magnitude.In multiple embodiments, a kind of reactant contains iron, and another kind of reactant contains fluorine.For example, a kind of reactant can be the iron compound that contains for example nitrate anion of anion or nitrite anions, and another kind of reactant can be the fluoride of hydrogen, for example ammonium acid fluoride.
In specific embodiment, the transition material of nanostructure forms by mix precursor material in its liquid atomic level.More specifically, implement to provide the method for the transition material that forms nanostructure.Described method comprises provides the first precursor material that contains metal-containing material.For example, metal-containing material comprises iron and/or other metal materials.The second precursor material is also provided.The second precursor material comprises oxidizing anions material, for example fluoride materials.The first precursor material and the second precursor material are characterised in that the trend being separated.The material that is separated has positive enthalpy of mixing.Under their stable state, the material that is separated separates to form the independently region being mainly made up of each homogenous material.Should understand because two kinds of precursor materials have the trend being separated, so do not use method as herein described to be difficult to manufacture with two kinds of precursor materials the glassy state transition material of nanostructure.
In atomization method, two kinds of precursor materials are fused into respectively liquid state, and are ejected into the described material of quenching in the cooling chamber of unstable or metastable condition.For example, the first precursor material and the second precursor material have different melt temperatures, and therefore can melt respectively, or fusing together at the temperature higher than fusing point.According to specific embodiment, mix and spray two kinds of precursor materials and can be undertaken by different orders.In a specific embodiment, in two kinds of precursor materials process before injection, put together as far as possible lately.In the time putting together with its liquid state, then two kinds of precursor materials are ejected in cooling chamber by single-nozzle.For example, nozzle impels two kinds of precursor materials to become undersized particle or nanometer farmland, and this allows to occur the mixing on atomic level, the material state mixing with " freezing " that quenches rapidly.
Or two kinds of precursor materials can be ejected into cooling chamber respectively by two or more nozzles, mix and only in cooling chamber, occur.In cooling chamber, two kinds of precursor materials mix to become the particle by the shaping of the nanostructure compositions of mixtures of two kinds of precursors under the size that is less than about 20nm.Because two kinds of precursor materials have the trend being separated, the particle of shaping or nanometer farmland need promptly cooling to rest on mixing and state nanostructure.In various embodiments, the particle of shaping or nanometer farmland are cooling with at least about 100 Kelvins speed per second.In a specific embodiment, it is per second that cooldown rate approaches 10000 Kelvins.For example, the particle of shaping or nanometer farmland cool to room temperature, and enough stable under the state of nanostructure and mixing.Cooling can carrying out in many ways.In one embodiment, cooling by cold inert gas is ejected in cooling chamber and is carried out.In another embodiment, coolingly undertaken by for example cold bronze drum or anvil of cooling surface.Then collect the particle or the nanometer farmland that form.For example, implement other method to use the particle that forms or nanometer farmland as the transition material in battery unit.
Need be appreciated that according to various embodiments of the present invention, transition material can use different technology to process.For example, can replace the particle or the nanometer farmland that produce formation with cooling chamber with cooling surface.In a specific embodiment, provide the cooling surface of rotation, owing to directly contacting with cooling surface, so the particle or the nanometer farmland that form are cooling rapidly.
As described in, the transition material of nanostructure can form by method of evaporating.In many evaporation techniques, precursor material is heated to it and has the temperature of obvious vapour pressure, then allows to deposit to the thickness of nano-scale in substrate.Such technology comprises thermal evaporation, electron beam evaporation, vapour deposition, close space sublimation etc.According to application, precursor material can have or not have the trend being separated.At its gaseous state separately, two kinds of precursor materials are in indoor mixing to form indoor composite material, and composite material is characterised in that the length dimension that is less than about 20nm.Cooling can be naturally or by contacting generation with cold surface or cold air.Then collect the material mixing.
In order to deposit the fluoride compound of iron as described herein, can implement the coevaporation of the material that contains iron and fluorine, two kinds of key components of matrix are mixed in gas phase, then deposit in substrate the nanometer farmland or the particle that there is about 20nm or less length dimension to form.In another embodiment, the source of each independent component of composition is evaporated respectively and is deposited in substrate, so that component forms independently layer.By keeping these layers for thering is enough thin size and suitable mass ratio, form the compound of expecting.Typically, every layer all very thin, typically at nanometer or the less order of magnitude.Select mass ratio to produce the mol ratio that has described in other places herein or reactive compound or the mixture of stoichiometric proportion.
An example of suitable evaporation technique is gas phase transmission deposition or flash distillation.It is by using the successive sedimentation that the membrane material of expectation is provided from the saturated with vapor carrier gas of sublimation source.In the directed substrate at a lower temperature of saturated mixture, cause hypersaturated state and the growth of film subsequently.In one embodiment, reactor adopts fluorine separately and the powder source of iron.Helium source is blown into hot helium to distil and transmit the powder that enters reactor, and in reactor, before depositing to cold substrate, component is mixed in gas phase.In the equipment of appropriate design, each powder provides by independent pipe, and passes through in the process of pipe in transmission, and powder is by hot helium or other gas-carrying evaporations.The non-limiting list of evaporation source can comprise LiF, FeF 3, FeF 2, LiFeF 3, Fe and Li.The source material of evaporation can be exposed to and pass through such as F of fluorine material 2, CF 4, SF 6, NF 3deng the course of reaction in the plasma or the environmental gas that produce.For FeLi af bthe suitable precursor of compound can comprise the fluoride of iron nano-particle, iron (II), fluoride, stainless steel, lithium metal, lithium fluoride or vapor precursor, for example F of iron (III) 2, CF 4, SF 6and NF 3.
Battery structure
The above-mentioned various elements that comprise collector body, anode, negative electrode and electrolytical battery of openly having described.Can use the battery design of traditional form.These had not only comprised cylindrical but also had comprised prismatic structure, and for example those are for those of consumer electronics device, electric motor car, Medical Devices, uninterrupted power supply etc.The size of these batteries and area occupied can to the battery of traditional form such as A, AA, AAA, C, 18650 etc. similar.
Although illustrate and mainly concentrate on solid electrolyte, should be appreciated that negative electrode disclosed herein also can use in the battery that uses liquid or gel electrolyte.Can use little multiple pileup battery structure.
In multiple embodiments, device has battery maintenance or battery controller device, such as battery charger and for controlled discharge and/or the such as interlock circuit of cut-ff voltage, cut-off capacity, electric current and temperature etc. of charge parameter.
Experimental result
Fig. 4: the LiF material relation of the little length dimension in battery performance and the layer structure of weighing by cathode volume energy density figure.Energy density by the speed at 10C and 120 ℃ between 1 to 4V constant-current discharge measure; All batteries have equal gross thickness (battery that for example length dimension is 35nm have double the number of plies that length dimension is the battery of 70nm).Battery passes through the Ti of sputter 30nm and the TiN of 40nm on Si wafer, then sputter cathode layer, and then the LiPON electrolyte of sputter 200nm is constructed.Li paper tinsel that 100 μ m are thick punched go out area be 0.3cm 2disk, and be held down to limit cell area.TiN and Li paper tinsel are electrically contacted for remaining on the measurement on the hot plate of 120 ℃.
The pantostrat that duplexer is manufactured Fe and LiF by the Thickness Ratio with 1:7 is manufactured, and this produces the discharge battery of the stoichiometric proportion with about Fe+3LiF.Along with the increase of length dimension, cathode performance is deteriorated, demonstrates the benefit that is low to moderate the nanostructure negative electrode (or cathode particles) that is less than 10nm.
The form of summing up data in Fig. 7-10 is as follows.Usefully notice that sulphur appropriate in negative electrode improves the quality load-carrying ability of electrode significantly.
Figure BDA00003529726000341
Fig. 5: the constant current charge of 3LiF+Fe negative electrode of 66nm and the figure of electric discharge at 120 ℃.Battery construct as described above and at 10C(dotted line) and 1C(solid line) C-speed under measure.88% equally high during with 1C of energy density in the time of 10C, voltage delay is 0.89V in the time of 1C, in the time of 10C, is 0.91V.The performance of the 3Li+Fe negative electrode of 66nm is deteriorated significantly along with C-speed has.
Fig. 6: the constant current charge of 3LiF+Fe negative electrode of 129nm and the figure of electric discharge at 120 ℃.Battery construct as described above and at 10C(dotted line) and 1C(solid line) C-speed under measure.58% equally large during with 1C of energy density in the time of 10C, voltage delay is 0.92V in the time of 10C, in the time of 1C, is 0.72V.Because negative electrode becomes thicker, performance is deteriorated even more obvious with speed, shows that performance is subject to mass transfer limit.
Fig. 7: its negative electrode is 134nm (3LiF+Fe+S 0.14) the figure of constant-current discharge of battery.Battery construct as described above and at 10C(dotted line) and 1C(solid line) C-speed under measure.When energy density in the time of 10C is 1C 83% of energy density, voltage delay is 0.72V in the time of 1C, in the time of 10C, is 0.88V.Compare with the negative electrode without sulfur content with similar thickness in Fig. 3, this negative electrode has much better rate capability, shows the significant benefit from 2%S content.
Fig. 8: its negative electrode is 134nm (3LiF+Fe+S 0.53) the figure of constant-current discharge of battery.Battery construct as described above and at 10C(dotted line) and 1C(solid line) C-speed under measure.When data in the time of 10C show than 1C, the capacity average voltage of high 106% energy density, 0.61V lags behind, and 0.75V and 74% energy efficiency during with respect to 1C, during with respect to 1C 64%.In statistical fluctuation, 10C during with respect to 1C performance in fact do not have deterioratedly, show that 7% sulfide loads substantially to have improved battery mass transfer.
As described above, according to embodiment of the present invention, cathode energy density is improved by the transition material of nanostructure.Fig. 9 provides the figure of the length dimension relation of the LiF material in battery performance and the layer structure of weighing by cathode volume energy density.Energy density by the speed at 10C and 120 ℃ with respect to Li 1 to 4V between constant-current discharge measure.This figure based on the battery of all measurements substantially there is identical gross thickness (battery that for example length dimension is 35nm have double the number of plies that length dimension is the battery of 70nm).As shown in Figure 9, when the length dimension that is less than 40nm and Fe when the length dimension of LiF is about 5nm, cathode energy density is about 1500Wh/L or larger.When the length dimension that is less than 20nm and Fe when the length dimension of LiF is less than about 5nm, cathode energy density is about 2500Wh/L or larger.Need be appreciated that because the nano-structured of particle can obtain high energy density.As described above, according to embodiment of the present invention, can formation nanostructure in many ways.
Figure 10 is the figure of the F material relation of the little length dimension in battery performance and the layer structure of weighing by cathode volume energy density.Energy density by completed cell structure with at the speed of 10C and 120 ℃ with respect to Li 1 to 4V between constant-current discharge measure.For the object of measuring, battery passes through at Si/SiO 2the Pt of sputter 50nm on wafer, then sputter cathode layer, then the LiPON electrolyte of 200nm is constructed.The top electrode of Fe sputters at definite region, and in charging process, Li is plated on Fe surface, and original position produces anode.Pt and Fe are electrically contacted for remaining on the measurement on the hot plate of 120 ℃.As described above, the pantostrat that duplexer is manufactured Fe and LiF by the Thickness Ratio with 1:3 is manufactured, and this produces the discharge battery of the stoichiometric proportion with about Fe+3LiF.Along with length dimension increases, cathode performance is deteriorated, demonstrates the benefit that is low to moderate the nanostructure negative electrode form that is less than 2nm.More specifically, as shown in figure 10, cathode energy density demonstrates with the graph of a relation of layer structure: along with length dimension reduces, every volume energy density increases." 20 × 0.5 " on x axle represent 20 layers (0.5nm Fe+1.5nm LiF), and " 20 × 1 " represent 20 layers (1nm Fe+3nm LiF), and " 10 × 2 " represent 10 layers (2nm Fe+6nm LiF).
Figure 11 provides the sectional view of the nanostructure transition material in the size of about 5nm.As what can see in Fig. 3 from above, the length dimension of about 5nm is unlike so good (low performance represents not as ideal material structure) of the transition material performance of the nanostructure under less size.For example, the figure shown in Figure 13-15 is a part for battery structure shown in Figure 1A and B.
Figure 12 provides the cross-sectional view of the nanostructure transition material in the size of about 2nm.At the smaller szie than Figure 11, the transition material of nanostructure shows better than the microstructure shown in Figure 11.
Figure 13 provides the cross-sectional view of the nanostructure transition material in the size of about 2nm.
Figure 14 is the figure that illustrates nano-structured transition material and keep the example of the benefit of Homogenizing of composition.For example, model of creation is to calculate the number reacting within what given atom certain distance of leaving one's post.Suppose reaction, for example Li+F+Fe → FeLiF is multi-step FeF 3a step in conversion lithiation, this model calculates distance L 1 and L2, and wherein L1 is the distance between F and Li, and L2 is the distance between F and Fe.As found out by calculating, in the time considering almost accurately stoichiometric proportion F/Fe=3 and F/Fe=2.5, the reaction of major part can complete in shorter distance.This can cause battery to have higher performance: higher efficiency, larger charge/discharge rates and higher conveying capacity.Therefore, glassy state/unbodied transition material should be prepared in the mode that keeps approaching desirable stoichiometric proportion in whole material.
Figure 15 represents the theoretical energy density with respect to the lithiumation conversion cathode material of standard Li anode.Overpotential is assumed to be 0.7V, considers activation loss and the intrinsic hysteresis of conversion reaction under mass transport losses, reasonable voltage.Figure 16 represents the theoretical specific energy with respect to the lithiumation conversion cathode material of standard Li anode.Again, overpotential is assumed to be 0.7V, considers activation loss and the intrinsic hysteresis of conversion reaction under mass transport losses, reasonable voltage.Because the value showing is theoretical value, so supposed the whole conversions under thermodynamic potential.
Figure 17 represents for the figure of initial 5 charge/discharge cycle of copper fluoride sample (voltage (relative standard's lithium electrode is measured) is with respect to the active capacity of cathode material).As directed, this active material of cathode demonstrates invertibity, only has medium hysteresis, high average voltage and approach complete capacity.
Figure 18 represents the electric discharge energy of the sample that contains the specific transitions metal alloy that is useful on transition material.Particularly, transition material composition is FeCo+LiF, FeMn+LiF, Fe 3co+LiF and control sample Fe+LiF.Discharge rate is 10C, the discharge voltage limit be with respect to standard metal lithium electrode 4 to 1V.Sample has the nominal thickness ratio of 7LiF:1M, and wherein M is metal, and it is alloy under non-control case.In each sample, form ten layers of metal (on said composition), ten layers of LiF are alternately inserted between metal level.As can be seen, 50%Fe-50%Co and the especially high specific capacity of 50%Fe-50%Mn offering sample.
In Figure 19, be following transition material offering sample capacity and the statistics that lags behind: FeCo+LiF, FeMn+LiF, Fe 3co+LiF and control sample Fe+LiF.C/3,1C that sample represents at given different colours, 10C(C/3 for white, 1C be that grey and 10C are black) speed under discharge, voltage range be with respect to metal lithium electrode 4 to 1V.

Claims (27)

1. a cathode material, comprises:
There is particle or the nanometer farmland of about 20nm or less intermediate value characteristic size,
Wherein, the particle of the metal that described particle or nanometer farmland comprise (i) chosen from Fe, cobalt, manganese, copper, nickel, bismuth and alloy thereof or nanometer farmland, and (ii) particle or the nanometer farmland of the fluoride of lithium.
2. cathode material claimed in claim 1, wherein, described metal is iron, manganese or cobalt, and the mol ratio of the fluoride of metal and lithium is approximately 2 to 8.
3. cathode material claimed in claim 1, wherein, described metal is copper or nickel, and the mol ratio of the fluoride of metal and lithium is about 1 to 5.
4. cathode material claimed in claim 1, wherein, described metal is iron, and described particle or nanometer farmland further comprise ferric flouride.
5. cathode material claimed in claim 1, wherein, described cathode material further comprises (iii) conductive additive.
6. cathode material claimed in claim 1, wherein, the intermediate value characteristic size on described particle or nanometer farmland is about 5nm or less.
7. cathode material claimed in claim 1, wherein, described particle or nanometer farmland are at about 1000nm 3volume in be uniform substantially.
8. a negative electrode, comprises:
(a) collector body,
(b) electrochemical active material, itself and described collector body electric connection and comprise: (i) metal component, and (ii) the lithium compound component of mixing with described metal group phase-splitting in about 20nm or less distance size,
Wherein, in the time of the compound of metal component described in being full of electric forming and the anion of described lithium compound, described electrochemical active material has about 350mAh/g or larger reversible specific capacity in the time utilizing lithium ion to discharge with the speed at least about 200mA/g.
9. negative electrode claimed in claim 8, wherein, described negative electrode further comprises the ion-electron conductor component of mixing.
10. negative electrode claimed in claim 8, wherein, the ion-electron conductor component of described mixing has glassy structure.
11. negative electrodes claimed in claim 8, wherein, described metal component is the alloy of transition metal, aluminium, bismuth or any these metals.
12. negative electrodes claimed in claim 8, wherein, described metal component comprises the metal grain with about 5nm or less intermediate value characteristic length.
13. negative electrodes claimed in claim 8, wherein, described lithium compound component is the fluoride of lithium.
14. negative electrodes claimed in claim 8, wherein, described lithium compound component comprises particle or the nanometer farmland with about 5nm or less intermediate value characteristic length size.
15. negative electrodes claimed in claim 8, wherein, it is that about 10nm is in the layer of 300 μ m that described electrochemical active material provides at thickness.
16. negative electrodes claimed in claim 8, wherein, in the time being full of electricity, described electrochemical active material has about 300mAh/g or larger reversible specific capacity in the time discharging with the speed at least about 6000mA/g by lithium ion.
17. negative electrodes claimed in claim 8, wherein, in the time that at the temperature of 100 ℃, the 1V of Li discharges to circulation between 4V and with the speed of about 200mAh/g active material of cathode relatively, described negative electrode shows lower than the average voltage of about 1V and lags behind.
Manufacture the method for battery for 18. 1 kinds, described method comprises:
(a) provide the negative electrode that comprises electrochemical active material, described electrochemical active material and collector body electric connection and comprise: (i) metal component, (ii) the lithium compound component of mixing with described metal group phase-splitting in about 20nm or less distance size, wherein, in the time of the compound of metal component described in being full of electric forming and the anion of described lithium compound, described electrochemical active material has about 350mAh/g or larger reversible specific capacity in the time utilizing lithium ion to discharge with the speed at least about 200mA/g; With
(b) cathode assembly and anode and solid electrolyte are to form described battery.
Method described in 19. claims 18, further comprises by the described electrochemical active material of solid-state synthetic preparation.
Method described in 20. claims 19, wherein, the synthetic precursor or the reactant that mix and grind described electrochemical active material of comprising of described solid phase.
Method described in 21. claims 19, wherein, described solid phase makes iron containing compounds and fluoride reaction synthetic comprising.
Method described in 22. claims 18, further comprises electrochemical active material described in the Evaporation preparation of the one or more of precursors by described electrochemical active material.
Method described in 23. claims 22, wherein said evaporation comprises makes to be selected from LiF, FeF 3, FeF 2, LiFeF 3, Fe and Li front evacuator body.
Method described in 24. claims 22, wherein said evaporation is included in to contain and is selected from F 2, CF 4, SF 6and NF 3the environment of gas in make the precursors reaction of evaporation.
Method described in 25. claims 18, further comprises by following steps and prepares described electrochemical active material:
Melt the one or more of precursors of described electrochemical active material;
Making the precursor atomization of fusing is particle; With
Cooling described particle to mix described metal component and described lithium compound component under about 20nm or less length dimension.
Method described in 26. claims 25, wherein said cooling to carry out at least about 100 Kelvins speed per second.
Method described in 27. claims 25, wherein said cooling by making described particle contact to carry out with the cooling surface of rotation.
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