CN101176225A - Method of making active materials for use in secondary electrochemical cells - Google Patents

Abstract

The present invention provides an electrochemical cell having a first electrode having an electrode active material containing at least one electrode active material charge-carrier, a second electrode, and an electrolyte containing at least one electrolyte charge-carrier. In the electrochemical cell's nascent state, the at least one electrolyte charge carrier differs from the at least one electrode active material charge-carrier.

Description

Making active materials for use in secondary electrochemical cells

The application requires the priority of the temporary patent application 60/729,932 of the priority of temporary patent application 60/666,132 of on March 28th, 2005 application and application on October 25th, 2005.

Technical field

The present invention relates to utilize electrolyte that contains charge carrier and the electrochemical cell that contains the positive electrode active materials of charge carrier, wherein in the nascent state (nascent state) of electrochemical cell, the charge carrier in the electrolyte is different from the charge carrier in the positive electrode active materials.

Background technology

Battery pack is made up of one or more electrochemical cells or battery pack, and wherein each battery generally includes positive pole, negative pole and electrolyte or other material that helps ionic charge carriers to move between negative pole and positive pole.After battery charge, cation, moves to negative pole from electrolyte to electrolyte simultaneously from positive pole.At interdischarge interval, cation, moves to positive pole from electrolyte to electrolyte simultaneously from negative pole.

Adopt the existing electrochemical cell of the electrode active material of alkali metal base to use the electrolyte that has dissolved corresponding alkali metal salt therein.In other words, the alkali metal in the electrode active material and alkali metal are identically (for example, to contain LiCoO ₂Battery in use LiPF ₆As electrolytic salt).Traditional concept is in order to form functional making active materials for use in secondary electrochemical cells, and this is essential.Because lithium (Li) is suitable for inserting the electrode (main because the circulation time lithium forms the stable SEI layer on graphite) of graphite-based (graphite-based) most, this for using the electrolytical needs of lithium base (lithium-based), need to use the insertion active material of lithium base as anodal (negative electrode) conversely.Owing to be difficult to the electrode material of synthetic this lithium base, or synthetic production cost height, this needs make the material of multiple lithium base fail to use in reality in electrochemical cell and the potential use.

Yet, usually can use the synthesis step of minority and the analog of less material and synthetic many these kinds insertions of production cost materials.Unfortunately, because traditional concept, just because of the misunderstanding of those skilled in the art in operating process, think and in the battery that contains positive electrode active materials that non-lithium base (non-lithium based), use the electrolyte of lithium base, thereby once attempted this electrode active material analog of application in anodal (negative electrode).Yet inventor's proof can be used the alkaline electrode of non-lithium base or the electrode of base (alkaline-based) in the electrolytical making active materials for use in secondary electrochemical cells of lithium base.

Summary of the invention

The invention provides a kind of novel making active materials for use in secondary electrochemical cells, its use contains the electrolyte of one or more (promptly at least a) charge carriers and contains the positive electrode active materials of one or more (promptly at least a) charge carriers, wherein in the nascent state of electrochemical cell, the charge carrier in the electrolyte is different from the charge carrier in the electrode active material.

In one embodiment, electrode active material (in its nascent state) is represented by following general formula:

A _aM _b(M′O) _c(XY ₄) _dO _eZ _f；

Wherein:

(i) A contains at least a element that can form cation and take off slotting (deintercalation or deinsertion) from active material when electrochemical cell charges, and 0＜a≤9;

(ii) M and M ' are selected from the group of being made up of transition metal, nontransition metal and composition thereof separately, and wherein M and M ' comprise at least a redox active element, and 1≤b≤6 and 0≤c≤1;

(iii) XY ₄Be selected from [O by X ' _4-x, Y ' _x], X ' [O _4-y, Y ' _2y], X " S ₄, [X _z, X ' _1-z] O ₄, WO ₄And composition thereof the group formed, wherein:

(a) X ' and X  independently are selected from the group of being made up of P, As, Sb, Si, Ge, V, S and composition thereof separately;

(b) X " is selected from the group of being made up of P, As, Sb, Si, Ge, V and composition thereof;

(c) W is selected from the group of being made up of V, Hf, Zr, Ti and composition thereof;

(d) Y ' is selected from the group of being made up of halogen, S, N and composition thereof, and wherein halogen is selected from periodic table the 17th family; And

(e) 0≤x≤3,0≤y≤2,0≤z≤1 and 0≤d≤3, wherein when e＞0, c and d (c, d)=0, when d＞0, e=0;

(iv) O is an oxygen, and 0≤e≤15, wherein when d＞0, and e=0; And

(v) Z is selected from the group of being made up of hydroxyl (OH), the halogen that is selected from periodic table the 17th family, nitrogen (N) and their mixture, and 0≤f≤4; And

Wherein, select M, X, Y, Z, a, b, c, x, y, z, d, e and f to keep the electric neutrality of nascent state or synthetic attitude (as-synthesized state) material.

In one embodiment, making active materials for use in secondary electrochemical cells is a kind of prismatic battery, and it has the coiled coil (spirally coiled) that is sealed in the cylindrical shell or (wound) electrode assemblie that is twining.In an optional execution mode, making active materials for use in secondary electrochemical cells is a rectangular cell, is wherein sealing volume core pattern (jellyroll-type) electrode assemblie in the cylindrical shell, and the cross section of this cylindrical shell is rectangle basically.In another embodiment, making active materials for use in secondary electrochemical cells is laminated-type (laminate-type) battery.

In each execution mode as herein described, electrode assemblie comprises the spacer (separator) that places between first electrode (positive pole) and relative second electrode (negative pole), be used to make first electrode and the second electrode electrically insulated from one another, wherein said first electrode contains above-mentioned electrode active material.

Electrochemical cell further comprises nonaqueous electrolyte.In the nascent state of electrochemical cell (promptly before battery circulates), nonaqueous electrolyte contains one or more charge carriers (Li for example ⁺), it is different from the element that is selected from positive electrode active materials A part.One preferred embodiment in, electrolyte is the nonaqueous electrolyte of lithium base.In other words, the positive electrode active materials of nascent state is not contain lithium.

Description of drawings

Fig. 1 is the cross sectional representation that nonaqueous electrolyte column Electrochemcial cell structures of the present invention is shown.

Fig. 2 is graphite/1M LiPF ₆(EC/DMC)/Na ₃V ₂(PO ₄) ₂F ₃The point diagram of the cathode specific capacity of rocking chair battery (cathode specific capacity) vs. cell voltage.

Fig. 3 is graphite/1M LiPF ₆(EC/DMC)/Na ₃V ₂(PO ₄) ₂F ₃The point diagram of the differential capacitance of rocking chair battery (differential capacity).

Fig. 4 is graphite/1M LiPF ₆(EC/DMC)/Na ₃V ₂(PO ₄) ₂F ₃The repeatedly point diagram of the cathode specific capacity of circulation of rocking chair battery.

Embodiment

Find that model electrochemical battery of the present invention has the advantage of known material of the prior art of being superior to and device.These advantages include but not limited to the one or more advantages in capacity increase, circulation ability enhancing, invertibity enhancing, ionic conductivity enhancing, conductivity enhancing, discharging efficiency (rate capability) enhancing and the cost reduction.Concrete advantage of the present invention and execution mode can be from the following detailed description of this paper obviously as seen.Yet should be appreciated that detailed description and specific embodiment be although understand that preferred embodiment, it is presented for purposes of illustration, rather than be used to limit the scope of the invention.

With reference to Fig. 1, shown making active materials for use in secondary electrochemical cells 10 with electrode active material, be preferably a kind of of the following general formula of this paper (I) expression.Battery 10 comprises coiled coil (spirallycoiled) that is sealed in closed container or (wound) electrode assemblie 12 that is twining, and described closed container is preferably the cylindrical shell 14 of rigidity.Electrode assemblie 12 comprises: first electrode or anodal 16 that is made of the following electrode active material of (amoung other things) this paper particularly; Relative second electrode or negative pole 18; And place spacer 20 between first electrode 16 and second electrode 18.Spacer 20 be preferably electric insulation, the ionic conductivity microporous barrier, and form by polymeric material, described polymeric material is selected from by polyethylene, poly(ethylene oxide), polyacrylonitrile and polyvinylidene fluoride, polymethyl methacrylate, polysiloxanes, their copolymer, and the group that constitutes of their mixture.

Electrode 16,18 comprises current-collector 22 and 24 respectively, is used to realize the current flowing between electrode 16,18 and the external load.Current-collector 22,24 all is that thickness is 5 μ m～100 μ m, is preferably conductive metal paper tinsel or the grid of 5 μ m～20 μ m, and described conductive metal for example is iron, copper, aluminium, titanium, nickel, stainless steel etc.Randomly, current-collector can be handled with oxide removing agents such as weak acid, and coats conductive coating to prevent to form the oxide of electric insulation on the surface of current-collector 22,24.The example of suitable coating compounds comprises the polymeric material that contains homodisperse conductive material (for example carbon), and this polymeric material comprises: acrylic resin, and it comprises acrylic acid and methacrylic acid and ester thereof, comprises ethylene-acrylic acid copolymer; Vinyl material, it comprises poly-(vinyl acetate) and vinylidene difluoride-hexafluoropropylene copolymer; Polyester, it comprises adipic acid-glycol copolymer; Polyurethane; Fluorubber; And their mixture.

Anodal 16 further are included at least one face of cathode collector 22, preferably form cathode film 26 on two faces of cathode collector 22, and the thickness of film 26 is 10 μ m～150 μ m, is preferably 25 μ m～125 μ m, so that battery 10 reaches optimum capacity.Cathode film 26 preferably is made of the electrode active material of the following general formula of this paper of 80wt%～95wt% (I) expression, the binding agent of 1wt%～10wt% and the conductive agent of 1wt%～10wt%.

Suitable binding agent comprises: polyacrylic acid, carboxymethyl cellulose; Diacetyl cellulose (diacetylcellulose); Hydroxypropyl cellulose; Polyethylene; Polypropylene; Ethylene-propylene-diene terpolymer; Polytetrafluoroethylene; Polyvinylidene fluoride; Butadiene-styrene rubber; Tetrafluoraoethylene-hexafluoropropylene copolymer; Polyvinyl alcohol; Polyvinyl chloride; Polyvinylpyrrolidone; Tetrafluoroethene-perfluoroalkyl vinyl ether copolymer; Vinylidene difluoride-hexafluoropropylene copolymer; Vinylidene fluoride-chlorotrifluoroethylcopolymer copolymer; Ethylene tetrafluoroethylene copolymer; Polychlorotrifluoroethylene; Vinylidene fluoride-five fluorine propylene copolymer; Propylene-TFE copolymer; Ethylene-chlorotrifluoro-ethylene copolymer; Vinylidene fluoride-hexafluoropropylene-TFE copolymer; Vinylidene fluoride-perfluorinated methyl ethylene ether-TFE copolymer; Ethylene-acrylic acid copolymer; Ethylene-methacrylic acid copolymer; Ethylene-methyl acrylate copolymer; The ethylene-methyl methacrylate methyl terpolymer; Butadiene-styrene rubber; Viton; Polybutadiene; And their mixture.In these materials, most preferably polyvinylidene fluoride and polytetrafluoroethylene.

Suitable conductive agent comprises: native graphite (as flake graphite etc.); Delanium; (thermal black) such as carbon black such as acetylene black, Ketzen black, channel black, furnace black, dim, thermalss; Conductive fiber such as carbon fiber and metallic fiber; Metal powder, for example fluorocarbons, copper, nickel etc.; And organic conductive material, as the polyphenylene derivative.

Negative pole 18 is by at least one face in anode collector 24, and preferably the negative electrode film 28 that forms on two faces of anode collector 24 constitutes.Negative electrode film 28 is made of the insertion material of 80wt%～95wt%, the binding agent of 2wt%～10wt% and the conductive agent of (choosing wantonly) 1wt%～10wt%.

Comprise at this suitable insertion active material: transition metal oxide, metal chalcogenide, carbon (as graphite) and their mixture, it can insert the alkali metal ion in the electrolyte of the nascent state that is present in electrochemical cell.

In one embodiment, insert material and be selected from the group of being made up of crystalline graphite and amorphous graphite and composition thereof, these graphite have one or more following character separately: by lattice crystal face (002) d-value (d of X-ray diffraction acquisition ₍₀₀₂₎) be 3.35 ～3.34 , comprise boundary value (3.35 ≤d ₍₀₀₂₎≤ 3.34 ), be preferably 3.354 ～3.370 , comprise boundary value (3.354 ≤d ₍₀₀₂₎≤ 3.370 ); The axial crystallite size (L of c-by the X-ray diffraction acquisition _c) be at least 200 , comprise boundary value (L _c〉=200 ), be preferably 200 ～1,000 , comprise boundary value (200≤L _c≤ 1,000 ), average grain diameter (P _d) be 1 μ m～30 μ m, comprise boundary value (1 μ m≤P _d≤ 30 μ m); Specific surface (SA) area is 0.5m ²/ g～50m ²/ g comprises boundary value (0.5m ²/ g≤SA≤50m ²/ g); Real density (p) is 1.9g/cm ³～2.25g/cm ³, comprise boundary value (1.9g/cm ³≤ p≤2.25g/cm ³).

Referring again to Fig. 1, do not electrically contact each other in order to ensure electrode 16,18, so electrode 16,18 becomes recess in the winding working procedure of manufacture process, spacer 20 " to be given prominence to " or it is stretched out each edge of negative pole 18, width outstanding or that stretch out is " a ".In one embodiment, 50 μ m≤a≤2,000 μ m.In order to ensure when charging alkali metal can be at the enterprising electroplating in the edge of negative pole 18, negative pole 18 " give prominence to " or it is stretched out each edge of anodal 16, width outstanding or that stretch out is " b ".In one embodiment, 50 μ m≤b≤2,000 μ m.

Cylindrical shell 14 comprises column parts 30, and parts 30 have blind end 32 and by edges corrugated 36 openends that limit, this blind end 32 is electrically connected with negative pole 18 by negative wire 34.During operating, column parts 30, especially blind end 32 conducts electricity, and it is for providing electrical connection between negative pole 18 and the external loading (not shown).Insulating element 38 is inserted between the electrode assemblie 12 and blind end 32 of coiled coil or winding.

Between positive pole 16 and external loading (not shown), provide electrical connection with the anodal 16 positive terminal assembly parts 40 that are electrically connected by positive wire 42.Preferably, overcharging (as the mode by positive temperature coefficient (PTC) element), high temperature and/or produce under the situation of excess air cylindrical shell 14 in, positive terminal assembly parts 40 are suitable for providing electrical connection between positive pole 16 and external loading/charging device.Suitable positive terminal assembly parts 40 are being signed and issued the U.S.Patent No.6 that gives people such as Iwaizono on October 14th, 2003,632,572; With sign and issue the U.S.Patent No.6 that gives people such as Okochi on December 23rd, 2003,667,132 is on the books.Washer part 42 is with the top and the positive terminal assembly parts 40 interlocks sealings (sealinglyengages) of column parts 30.

The nonaqueous electrolyte (not shown) of the transmission ionic charge carriers between positive pole 16 and negative pole 18 in electrochemical cell 10 chargings and interdischarge interval is provided.This electrolyte comprises nonaqueous solvents and the alkali metal salt that is dissolved in wherein, and it can be gone up at negative pole (most preferably being lithium salts) and form the stable SEI layer.In the nascent state of electrochemical cell (promptly before battery circulates), nonaqueous electrolyte contains the charge carrier beyond the element that is selected from electrode active material component A.

Suitable solvent comprises: cyclic carbonate ester, as ethylene carbonate, propene carbonate, butylene or vinylene carbonate; Non-ring manganese ester is as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate or dipropyl carbonate; The aliphatic carboxylic acid esters, is as methyl formate, methyl acetate, methyl propionate or ethyl propionate; Gamma lactone is as gamma-butyrolacton; Acyclic ether, as 1,2-dimethoxy-ethane, 1,2-diethoxyethane or (ethoxymethyl) oxidative ethane; Cyclic ethers is as oxolane or 2-methyltetrahydrofuran; Organic aprotic solvent, as dimethyl sulfoxide (DMSO), 1, the 3-dioxolanes, formamide, acetamide, dimethyl formamide, dioxolanes, acetonitrile, propionitrile, nitromethane, ethylene glycol diethyl ether (ethyl monoglyme), phosphotriester (phospheric acidtriester), trimethoxy-methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone (1,3-dimethyl-2-imidazolidinone), 3-methyl-2-oxazolidone, the propylene carbonate ester derivant, tetrahydrofuran derivatives, ether, 1,3-propane sultone, methyl phenyl ethers anisole, dimethyl sulfoxide (DMSO) and N-methyl pyrrolidone; And their mixture.Be preferably the mixture of cyclic carbonate ester and non-ring manganese ester or cyclic carbonate ester, non-ring manganese ester and aliphatic carboxylic acid esters,'s mixture.

Suitable alkali metal salt, especially lithium salts comprises: LiClO ₄LiBF ₄LiPF ₆LiAlCl ₄LiSbF ₆LiSCN; LiCF ₃SO ₃LiCF ₃CO ₂Li (CF ₃SO ₂) ₂LiAsF ₆LiN (CF ₃SO ₂) ₂LiB ₁₀Cl ₁₀Lower aliphatic carboxylic acid lithium; LiCl; LiBr; LiI; Chlorine boron lithium (chloroboran of lithium); The tetraphenyl borate lithium; Imide li; And their mixture.Electrolyte preferably comprises LiPF at least ₆

As mentioned above, cathode film 26 contains a kind of positive electrode active materials, and wherein in the nascent state of electrochemical cell, the charge carrier in the positive electrode active materials is different from the charge carrier in the electrolyte.As used herein, " positive electrode active materials charge carrier " means the element that can form cation and take off slotting (deintercalation or deinsertion) from active material when containing the electrochemical cell initial charge of this element.As used herein, " electrolyte charge carrier " means the ion in the electrolyte that is present in the nascent state electrochemical cell.

In an embodiment of the invention, the positive electrode active materials of nascent state is represented by following general formula (I):

A _aM _b(M′O) _c(XY ₄) _dO _eZ _f(I)

For all execution modes as herein described, before electrochemical cell circulated, electrode active material as herein described was in its first condition or synthetic attitude.Select the component of electrode active material, make the electric neutrality of keeping electrode active material.The stoichiometric number of one or more elements of composition can be a non integer value.

For all execution modes as herein described, component A contains at least a positive electrode active materials charge carrier.Except as otherwise noted, A contains at least a element, and it can form cation and take off slotting (deintercalation or deinsertion), wherein 0＜a≤9 from active material when containing the electrochemical cell initial charge of this element.In one embodiment, A is selected from the group be made up of periodic table I and II family element and their mixture (as [A _a=A _{A-a '}A ' _{A '}, wherein A and A ' are selected from the group of being made up of periodic table I and II family element separately, and A and A ' are different, and a '＜a).In an inferior execution mode (subembodiment), under the synthetic attitude or nascent state of material, A does not comprise lithium (Li).In another inferior execution mode, under the synthetic attitude or nascent state of material, A does not comprise lithium (Li) or sodium (Na).

" family " as herein described is meant defined subgroup number (being columns) in the present IUPAC periodic table.(as referring to, signed and issued on October 24th, 2000, people's such as Barker United States Patent (USP) 6,136,472 is incorporated this paper in the reference mode.) in addition, the kind of element, material or other composition that concrete composition or constituents mixt are selected from means all possible subspecies class combination that comprises cited composition and composition thereof.

Preferably, should contain the component A of q.s (a), carry out oxidation/reduction with all " redox active (redox active) " elements that allow component M (as this paper with undefined).Shift out the component A of a certain amount of (a) from electrode active material, such as below this paper definition, what be accompanied by is the change of the oxidation state of at least a " redox active " element in the active material.The amount that is used for the redox active material of oxidation/reduction in the active material has determined the amount of extensible component A.In general the application, this notion is well known in the art, as is signed and issued on October 16th, 1984 United States Patent (USP) 4,477,541 of Fraioli; With signed and issued on October 24th, 2000, people's such as Barker United States Patent (USP) 6,136,472 is incorporated these two pieces of documents into this paper in the reference mode.

In all execution modes as herein described, component A can be replaced by component D non-equivalence (aliovalent) with the stoichiometry that equates or do not wait or (isovalent) of equal value replaces, wherein:

$\left(a\right){,A}_a=\left[A_{a-g^{\′}}{D}_{\frac{h}{V^D}}\right],$

(b) D is the different element of alkali metal charge carrier that is present in the electrochemical cell with nascent state in the electrolyte;

(c) V ^DIt is the oxidation state of component D;

(d) V ^A=V ^DOr V ^A≠ V ^D

(e) g=h or f ≠ h; With

(f) g, h＞0 and g≤a.

" of equal value replace " is meant with the element on the given crystallization site of the element replacement of identical oxidation state (as using Mg ²⁺Replace Ca ²⁺)." non-equivalence replacement " is meant with the element of different oxidation state and replaces element on the given crystallization site one (as using Mg ²⁺Replace Na ⁺).

Preferably, component D is preferred suitable with the atomic radius of the component A basically at least a element of its atomic radius.In one embodiment, D is at least a transition metal.The example that is used for the transition metal of component D in this article includes but not limited to Nb (niobium), Zr (zirconium), Ti (titanium), Ta (tantalum), Mo (molybdenum), W (tungsten) and their mixture.In another embodiment, component D be valence state 〉=2+ and atomic radius basically with substituted component (as, M and/or A) suitable at least a element.Unless certain illustrated is arranged in addition, variable as herein described, equal ("=") on the algebra, be less than or equal to ("≤") or more than or equal to (" 〉=") number be comprise approximate or function on be equivalent to the numerical value or the number range of described number.

About component A, the example of this element includes but not limited to Nb (niobium), Mg (magnesium) and Zr (zirconium).Preferably, the valence state of D or oxidation state (V ^D) greater than the valence state of the component that is replaced by component D (as component M and/or component A) or oxidation state the summation of oxidation state of the element of this component (or form).

For component A as herein described partly by component D all execution modes that replace of equal value, A can by etc. the component D of stoichiometry replace g wherein, h＞0; G≤a, and g=h.

When component A partly by component D is of equal value when replacing, and g ≠ h then needs to regulate in the active material other component (as A, M, XY ₄The stoichiometry of one or more and Z) is to keep electric neutrality.

For all execution modes that component A as herein described is partly replaced by component D non-equivalence, component A can be replaced by the component D of " oxidation " equivalent, wherein g=h; G, h＞0; And g≤a.

When component is partly replaced by component D non-equivalence, and d ≠ f, then need to regulate other component in the active material (as A, M, (M ' O), XY ₄, O and Z) in one or more stoichiometry, to keep electric neutrality.

Return general formula (I), in all execution modes of this paper, at least a among M and the M ' comprises at least a redox active element, and 1≤b≤6.In one embodiment, component M and M ' are selected from the group of being made up of transition metal, nontransition metal and composition thereof separately, wherein.Term used herein " redox active element " comprises when electrochemical cell operates under the normal operation condition can carry out those elements that oxidation/reduction reaction reaches another oxidation state.The expection voltage of term used herein " normal operation condition " when being meant battery charge, it depends on the material of forming battery.

The redox active element that is used for component M and M ' herein includes but not limited to the element of 11 families of periodic table the 4th family to the, and the nontransition metal of selecting, it includes but not limited to Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Si (silicon), Sn (tin), Pb (lead) and composition thereof.For each execution mode as herein described, M and/or M ' can comprise that the mixture of the oxidation state of selected element is (as, M/M '=Mn ²⁺Mn ⁴⁺).

In one embodiment, component M and/or M ' are the redox active elements.In an inferior execution mode, M is a kind of redox active element, and it is selected from by Ti ²⁺, V ²⁺, Cr ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Mo ²⁺, Si ²⁺, Sn ²⁺And Pb ²⁺The group of forming.In another inferior execution mode, M is a kind of redox active element, and it is selected from by Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺And Nb ³⁺The group of forming.

In another embodiment, component M and/or M ' comprise one or more redox active elements and (choosing wantonly) one or more non-oxide reducing activity elements." the non-oxide reducing activity element " of indication comprises and can form stable active material herein, and when electrode active material operates under the normal operation condition, do not carry out the element of oxidation/reduction reaction.

Can be used for non-oxide reducing activity element of the present invention includes but not limited to: be selected from the 2nd family's element, especially Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium); The 3rd family's element, especially Sc (scandium), Y (yttrium), and lanthanide series, especially La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium); The 12nd family's element, especially Zn (zinc) and Cd (cadmium); The 13rd family's element, especially B (boron), Al (aluminium), Ga (gallium), In (indium), TI (thallium); The 14th family's element, especially C (carbon) and Ge (germanium), the 15th family's element, especially As (arsenic), Sb (antimony) and Bi (bismuth); The 16th family's element, especially Te (tellurium); And their mixture.

In one embodiment, M and/or M '=MI _nMII _o, wherein 0＜o+n≤b, and o and n all greater than zero (0＜o, n), wherein MI and MII each independently be selected from the group of forming by redox active element and non-oxide reducing activity element, wherein MI and MII at least one be redox active.MI can be by stoichiometry or equivalence or non-equivalence replacements such as MII with not waiting stoichiometry.

For MI partly by MII all execution modes that replace of equal value, MI can by etc. the MII of stoichiometry replace so M=MI _N-oMII _oFor MI partly by the unequal execution mode of stoichiometry of MII replacement of equal value and MI and MII, M=MI _N-oMII _pAnd o ≠ p then needs to regulate in the active material one or more other components (as A, D, XY ₄, O and Z) stoichiometry, to keep electric neutrality.

Partly replaced and the MI of equivalent is replaced by the MII of equivalent for MI by the MII non-equivalence, so M=MI _N-oMII _o, one or more other components are (as A, D, XY in the necessary adjusting active material ₄, O and Z) in stoichiometry, to keep electric neutrality.Yet MI can partly be replaced by the MII non-equivalence, and the replacement mode replaces MI with " oxidation " equivalent MII

(as, therefore, $M={\mathrm{MI}}_{n-\frac{o}{V^{\mathrm{MI}}}}{\mathrm{MII}}_{\frac{o}{V^{\mathrm{MII}}}}$ V wherein ^MIBe the oxidation state of MI, V ^MIIBe the oxidation state of MII).

In an inferior execution mode, MI is selected from the group of following composition: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Si, Pb, Mo, Nb and composition thereof, and MII is selected from the group of following composition: Be, Mg, Ca, Sr, Ba, Sc, Y, Zn, Cd, B, Al, Ga, In, C, Ge and composition thereof.In this Asia execution mode, MI can be replaced by MII equivalence or non-equivalence.

In another inferior execution mode, MI is partly by MII replacement of equal value.Aspect one in this Asia execution mode, MI is selected from the group of following composition: Ti ²⁺, V ²⁺, Cr ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Mo ²⁺, Si ²⁺, Sn ²⁺, pb ²⁺And composition thereof, and MII is selected from the group of following composition: Be ²⁺, Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, Zn ²⁺, Cd ²⁺, Ge ²⁺And composition thereof.Aspect another of this Asia execution mode, MI is selected from the above-mentioned group that limits, and MII is selected from by Be ²⁺, Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺And composition thereof the group formed.Aspect another of this Asia execution mode, MI is selected from the above-mentioned group that limits, and MII is selected from by Zn ²⁺, Cd ²⁺And composition thereof the group formed.Aspect another of this Asia execution mode, MI is selected from by Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof the group formed, MII is selected from by Sc ³⁺, Y ³⁺, B ³⁺, Al ³⁺, Ga ³⁺, In ³⁺And composition thereof the group formed.

In another embodiment, MI is partly replaced by the MII non-equivalence.Aspect one in this Asia execution mode, MI is selected from the group of following composition: Ti ²⁺, V ²⁺, Cr ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Mo ²⁺, Si ²⁺, Sn ²⁺, pb ²⁺And composition thereof, and MII is selected from by Sc ³⁺, Y ³⁺, B ³⁺, Al ³⁺, Ga ³⁺, In ³⁺And composition thereof the group formed.Aspect in this Asia execution mode another, MI is that oxidation state is the redox active element of 2+, and it is selected from the group of above-mentioned qualification, and MII is selected from by alkali metal, Cu ¹⁺, Ag ¹⁺And composition thereof the group formed.Aspect in this Asia execution mode another, MI is selected from the group of following composition: Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof, and MII is selected from the group of following composition: Be ²⁺, Mg ²⁺, Ca ²⁺, Sr ²⁺, B ²⁺, Zn ²⁺, Cd ²⁺, Ge ²⁺And composition thereof.Aspect in this Asia execution mode another, MI is that oxidation state is the redox active element of 3+, and it is selected from the group of above-mentioned qualification, and MII is selected from by alkali metal, Cu ¹⁺, Ag ¹⁺And composition thereof the group formed.

In another embodiment, M and/or M '=M1 _qM2 _rM3 _s, wherein:

(i) M1 is that oxidation state is the redox active element of 2+;

(ii) to be selected from by oxidation state be the redox active element of 1+ and the group that non-oxide reducing activity element is formed to M2;

(iii) to be selected from by oxidation state be the group that 3+ or higher redox active element and non-oxide reducing activity element are formed to M3; And

(iv) q, r and s at least one greater than 0, and M1, M2 and M3 at least one have redox active.

In an inferior execution mode, M1 is replaced by the M2 of equivalent and/or M3, so q=q-(r+s).In this Asia execution mode, then need to regulate one or more other components in the active material (as A, XY ₄And Z) stoichiometry in is to keep electric neutrality.

In another inferior execution mode, M1 is by the M of " oxidation activity " of equivalent ²And/or M ³Replace (as, therefore $M={M1}_{q-\frac{r}{V^{M1}}-\frac{s}{V^{M1}}}{M2}_{\frac{r}{V^{M2}}}{M3}_{\frac{s}{V^{M3}}}$

V wherein ^M1Be the oxidation state of M1, V ^M2Be oxidation state and the V of M2 ^M3Be the oxidation state of M3).

In an inferior execution mode, M1 is selected from the group of following composition: Ti ²⁺, V ²⁺, Cr ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Mo ²⁺, Si ²⁺, Sn ²⁺, pb ²⁺And composition thereof; M2 is selected from by Cu ¹⁺, Ag ¹⁺And composition thereof the group formed; M3 is selected from the group of following composition: Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof.In another inferior execution mode, M1 and M3 are selected from above-mentioned described group respectively, and M2 is selected from the group of following composition: Li ¹⁺, K ¹⁺, Na ¹⁺, Ru ¹⁺, Cs ¹⁺And composition thereof.

In another inferior execution mode, M1 is selected from the group of following composition: Be ²⁺, Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, Zn ²⁺, Cd ²⁺, Ge ²⁺And composition thereof; M2 is selected from by Cu ¹⁺, Ag ¹⁺And composition thereof the group formed; M3 is selected from the group of following composition: Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof.In another inferior execution mode, M1 and M3 are selected from above-mentioned described group respectively, and M2 is selected from the group of following composition: Li ¹⁺, K ¹⁺, Na ¹⁺, Ru ¹⁺, Cs ¹⁺And composition thereof.

In another inferior execution mode, M1 is selected from the group of following composition: Ti ²⁺, V ²⁺, Cr ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Mo ²⁺, Si ²⁺, Sn ²⁺, Pb ²⁺And composition thereof; M2 is selected from by Cu ¹⁺, Ag ¹⁺And composition thereof the group formed; M3 is selected from the group of following composition: Sc ³⁺, Y ³⁺, B ³⁺, Al ³⁺, Ga ³⁺, In ³⁺And composition thereof.In another inferior execution mode, M1 and M3 are selected from above-mentioned described group respectively, and M2 is selected from the group of following composition: Li ¹⁺, K ¹⁺, Na ¹⁺, Ru ¹⁺, Cs ¹⁺And composition thereof.

In all execution modes as herein described, component XY ₄Be the polyanion that is selected from the group of following composition: X ' [O _4-x, Y ' _x], X ' [O _4-y, Y ' _2y], X " S ₄, [X _z, X ' _1-z] O ₄, WO ₄And composition thereof, wherein:

(a) X ' and X  each independently be selected from the group of following composition: P, As, Sb, Si, Ge, V, S and composition thereof;

(b) X " is selected from the group of following composition: P, As, Sb, Si, Ge, V and composition thereof;

(c) W is selected from the group of following composition: V, Hf, Zr, Ti and composition thereof;

(d) Y ' is selected from the group of following composition: halogen, S, N and composition thereof;

(e) 0≤x≤3,0≤y≤2,0≤z≤1, and 0≤d≤3, when e＞0, c and d (c, d)=0, when d＞0, e=0.

In one embodiment, XY ₄Be selected from the group of following composition: X ' O _4-xY ' _x, X ' O _4-yY ' _2yAnd composition thereof, and x and y all be 0 (x, y=0).Except as otherwise noted, XY ₄Be the polyanion in the group that is selected from following composition: PO ₄, SiO ₄, GeO ₄, VO ₄, AsO ₄, SbO ₄, SO ₄And composition thereof.XY ₄Be preferably PO ₄(phosphate radical) or PO ₄Mix with above-mentioned another kind is anionic that (that is, wherein X ' is not P, and Y ' is not O, or either way has, as defined above).In one embodiment, XY ₄Comprise about 80% or more phosphate radical, and one or more above-mentioned anion of about at the most 20%.

In another inferior execution mode, XY ₄Be selected from the group of following composition: X ' [O _4-xY ' _x], X ' [O _4-yY ' _2y] and composition thereof, and 0＜x≤3,0＜y≤2, wherein component XY ₄In a part of oxygen (O) replaced by halogen, S, N or its mixture.

In another inferior execution mode, XY ₄=WO ₄, wherein W is selected from the group of following composition: V, Hf, Zr, Ti and composition thereof.In another inferior execution mode, W is selected from the group of being made up of Zr and Ti.

In all execution modes of this paper, component Z (when existing) is selected from the group of following composition: OH (hydroxyl), nitrogen (N), halogen or its mixture, wherein 0≤f≤4.In one embodiment, Z is selected from the group of following composition: OH, F (fluorine), Cl (chlorine), Br (bromine) and their mixture.In another embodiment, Z is OH.In another execution mode, Z is the mixture of F or F and OH, Cl or Br.

Select the composition of electrode active material and the stoichiometric number of this component, to keep the electric neutrality of electrode active material.The stoichiometric number of the element of one or more compositions can be a non integer value.Preferably, component XY ₄Be to have-2 ,-3 or the anion of-4 electric charges during as the unit component, it depends on X ', X ", the selection of X , Y ' and x and y.Work as XY ₄When being the mixture of polyanion, for example above-mentioned preferred phosphate/phosphate substituent, XY ₄Anionic net charge can be a non integer value, and it depends on the independent radicals X Y in the mixture ₄Electric charge and composition.

In a special inferior execution mode, cathode film 26 contains the electrode active material by following general formula (II) expression:

A _aM _b(XY ₄) _dZ _f， (II)

(i) component A, M and Z as mentioned above, 0＜a≤9,1≤b≤3 and 0≤f≤4 wherein; And

(ii) XY ₄Be selected from the group of following composition: X ' [O _4-x, Y ' _x], X ' [O _4-y, Y ' _2y], X " S ₄, [X _z, X ' _1-z] O ₄, and composition thereof, wherein:

(a) X ' and X  each independently be selected from the group of following composition: P, As, Sb, Si, Ge, V, S and composition thereof;

(b) X " is selected from the group of following composition: P, As, Sb, Si, Ge, V and composition thereof;

(c) Y ' is selected from the group of following composition: halogen, S, N and composition thereof;

(d) 0≤x≤3,0≤y≤2,0≤z≤1, and 1≤d≤3; And

Wherein select A, M, X, Y, Z, a, b, x, y, z and f to keep the electric neutrality of nascent state or synthetic attitude material.

In a concrete inferior execution mode, the M of general formula (II) is selected from the group of following composition: Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof, (be preferably V ³⁺), XY ₄=PO ₄, d=3, and f=0.In another inferior execution mode, the M of general formula (II) is selected from the group of following composition: Ti ²⁺, V ²⁺, Cr ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Mo ²⁺, Si ²⁺, Sn ²⁺, pb ²⁺, and composition thereof, (be preferably Fe ²⁺), XY ₄=PO ₄, d=1, and f=0.

In a concrete inferior execution mode, the M of general formula (II) is selected from the group of following composition: Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof, (be preferably V ³⁺), XY ₄=PO ₄And d=2.

The method of the electrode active material of preparation shown in general formula (II) is known in the art, and description is arranged in following patent documentation: people's such as announcement on July 26 calendar year 2001 Barker WO 01/54212, people's such as announcement on March 26th, 1998 Barker WO 98/12761, people's such as announcement on January 6th, 2000 Barker WO 00/01024, people's such as announcement on June 2nd, 2000 Barker WO 00/31812, people's such as announcement on September 28th, 2000 Barker WO 00/57505, people's such as announcement on June 6th, 2002 Barker WO02/44084, people's such as announcement on October 16th, 2003 Saidi WO 03/085757, people's such as announcement on October 16th, 2003 Saidi WO 03/085771, people's such as announcement on October 23rd, 2003 Saidi WO03/088383, signed and issued people's such as Barker U.S. Patent application 6 on March 4th, 2003,528,033, signed and issued people's such as Barker U.S. Patent application 6 on May 14th, 2002,387,568, people's such as announcement on February 2nd, 2003 Barker U.S.Publication No.2003/0027049, people's such as announcement on December 19th, 2002 Barker U.S.Publication No.2002/0192553, people's such as people's such as announcement on September 11st, 2003 Barker U.S.Publication No.2003/0170542 and announcement on July 10th, 2003 Barker U.S.Publication No.2003/1029492, above-mentioned all instruction contents are all incorporated this paper in the reference mode.

In this Asia execution mode by general formula (I) and (II) non-limiting example of active material of expression comprise following cited:

Na _0.95Co _0.8Fe _0.15Al _0.05PO ₄，Na _1.025Co _0.85Fe _0.05Al _0.025Mg _0.05PO ₄，

Na _1.025Co _0.80Fe _0.10Al _0.025Mg _0.05PO ₄，Na _1.025Co _0.45Fe _0.45Al _0.025Mg _0.05PO ₄，

Na _1.025Co _0.75Fe _0.15Al _0.025Mg _0.05PO ₄，Na _1.025Co _0.7(Fe _0.4Mn _0.6) _0.2Al _0.025Mg _0.05PO ₄，

Na _1.025Co _0.75Fe _0.15Al _0.025Mg _0.05PO ₄，Na _1.025Co _0.85Fe _0.05Al _0.025Mg _0.05PO ₄，

Na _1.025Co _0.7Fe _0.08Mn _0.12Al _0.025Mg _0.05PO ₄，NaCo _0.75Fe _0.15Al _0.025Ca _0.05PO _3.975F _0.025，

NaCo _0.80Fe _0.10Al _0.025Ca _0.05PO _3.975F _0.025，Na _1.25Co _0.6Fe _0.1Mn _0.075Mg _0.025Al _0.05PO ₄，

Na _1.0Na _0.25Co _0.6Fe _0.1Cu _0.075Mg _0.025Al _0.05PO ₄.Na _1.025Co _0.8Fe _0.1Al _0.025Mg _0.075PO ₄，

Na _1.025Co _0.6Fe _0.05Al _0.12Mg _0.0325PO _3.75F _0.25，

Na _1.025Co _0.7Fe _0.1Mg _0.0025Al _0.04Po _3.75F _0.25，Nla _0.75Co _0.5Fe _0.05Mg _0.015Al _0.04PO ₃F，

Na _0.75Co _0.5Fe _0.025Cu _0.025Be _0.015Al _0.04PO ₃F，

Na _0.75Co _0.5Fe _0.025Mn _0.025Ca _0.015Al _0.04PO ₃F，

Na _1.025Co _0.6Fe _0.05B _0.12Ca _0.0325PO _3.75F _0.25，

Na _1.025Co _0.65Fe _0.05Mg _0.0125Al _0.1PO _3.75F _0.25，

Na _1.025Co _0.65Fe _0.05Mg _0.055Al _0.14PO _3.975F _0.025，

Na _1.075Co _0.8Fe _0.05Mg _0.025Al _0.05PO _3.975F _0.025，NaCo _0.8Fe _0.1Al _0.025Mg _0.05PO _3.975F _0.025，

Na _0.25Fe _0.7Al _0.45PO ₄，NaMnAl _0.067(PO ₄) _0.8(SiO ₄) _0.2，Na _0.95Co _0.9Al _0.05Mg _0.05PO ₄，

Na _0.95Fe _0.8Ca _0.15Al _0.05PO ₄，Na _0.25MnBe _0.425Ga _0.3SiO ₄，NaMn _0.6Ca _0.375Al _0.1PO ₄，

Na _0.25Al _0.25Mg _0.25Co _0.75PO ₄，Na _0.55B _0.15Ni _0.75Ba _0.25PO ₄.

Na _1.025Co _0.9Al _0.025Mg _0.05PO ₄，Na _0.95Co _0.9Al _0.05Mg _0.05PO ₄，

Na _0.95Fe _0.8Ca _0.15Al _0.05PO ₄，Na _1.025Co _0.7(Fe _0.4Mn _0.6) _0.2Al _0.025Mg _0.05PO ₄，，

Na _1.025Co _0.8Fe _0.1Al _0.025Mg _0.05PO ₄，Na _1.025Co _0.9Al _0.025Mg _0.05PO ₄，

Na _1.025Co _0.75Fe _0.15Al _0.025Mg _0.025PO ₄，

NaCo _0.75Fe _0.15Al _0.025Ca _0.05PO _3.975F _0.025，NaCo _0.9Al _0.025Mg _0.05PO _3.975F _0.025，

Na _0.75Co _0.625Al _0.25PO _3.75F _0.25，Na _1.075Co _0.8Cu _0.05Mg _0.025Al _0.05PO _3.975F _0.025，

Na _1.075Fe _0.8Mg _0.075Al _0.05PO _3.975F _0.025，Na _1.075Co _0.9Mg _0.075Al _0.05PO _3.975F _0.025，

Na _1.0255Co _0.8Mg _0.1Al _0.05PO _3.975F _0.025，NaCo _0.7Fe _0.2Al _0.025Mg _0.05PO _3.975F _0.025，

Na ₂Fe _0.8Mg _0.2PO ₄F；Na ₂Fe _0.5Co _0.5PO ₄F；Na ₃CoPO ₄F ₂；KFe(PO ₃F)F；

Na ₂Co(PO ₃F)Br ₂；Na ₂Fe(PO ₃F ₂)F；Na ₂FePO ₄Cl；Na ₂MnPO ₄OH；Na ₂CoPO ₄F；

Na ₂Fe _0.5Co _0.5PO ₄F；Na ₂Fe _0.9Mg _0.1PO ₄F；Na ₂Fe _0.8Mg _0.2PO ₄F；

Na _1.25Fe _0.9Mg _0.1PO ₄F _0.25；Na ₂MnPO ₄F；Na ₂CoPO ₄F；K ₂Fe _0.9Mg _0.1P _0.5As _0.5O ₄F；

Na ₂MnSbO ₄OH；Na ₂Fe _0.6Co _0.4SbO ₄Br；Na ₃CoAsO ₄F ₂；NaFe(AsO ₃F)Cl；

Na ₂Co(As _0.5Sb _0.5O ₃F)F ₂；K ₂Fe(AsO ₃F ₂)F；Na ₂MSbO ₄F；Na ₂FeAsO ₄OH；

Na ₄Mn ₂(PO ₄) ₃F；Na ₄FeMn(PO ₄) ₃OH；Na ₄FeV(PO ₄) ₃Br；Na ₃VAl(PO ₄) ₃F；

K ₃VAl(PO ₄) ₃Cl；Na ₂KTiFe(PO ₄) ₃F；Na ₄Ti ₂(PO ₄) ₃Br；Na ₃V ₂(PO ₄) ₃F ₂；

Na ₆FeMg(PO ₄) ₃OH；Na ₄Mn ₂(AsO ₄) ₃F；K ₄FeMn(AsO ₄) ₃OH；

Na ₄FeV(P _0.5Sb _0.5O ₄) ₃Br；Na ₂KAlV(AsO ₄) ₃F；K ₃VAl(SbO ₄) ₃Cl；Na ₃TiV(SbO ₄) ₃F；

Na ₂FeMn(P _0.5As _0.5O ₃F) ₃；Na ₄Ti ₂(PO ₄) ₃F；Na _3.25V ₂(PO ₄) ₃F _0.25；Na ₄Fe ₂(PO ₄) ₃F _0.75；

Na _6.5Fe ₂(PO ₄) ₃(OH)Cl _0.5；K ₈Ti ₂(PO ₄) ₃F ₃Br ₂；K ₈Ti ₂(PO ₄) ₃F ₅；Na ₄Ti ₂(PO ₄) ₃F；

Na _2.25V ₂(PO ₄) ₃F _0.5Cl _0.75；K _3.25Mn ₂(PO ₄) ₃OH _0.25；Na _2.25KTiV(PO ₄) ₃(OH) _1.25Cl；

Na ₈Ti ₂(PO ₄) ₃F ₃Cl ₂；Na ₇Fe ₂(PO ₄) ₃F ₂；Na ₅FeMg(PO ₄) ₃F _2.25Cl _0.75；

Na _5.5TiMn(PO ₄) ₃(OH) ₂Cl _0.5；Na ₃K _4.5MnCa(PO ₄) ₃(OH) _1.5Br；K ₉FeBa(PO ₄) ₃F ₂Cl ₂；

Na ₇Ti ₂(SiO ₄) ₂(PO ₄)F ₂；Na ₈Mn ₂(SiO ₄) ₂(PO ₄)F ₂Cl；Na ₃K ₂V ₂(SiO ₄) ₂(PO ₄)(OH)Cl；

Na ₄Ti ₂(SiO ₄) ₂(PO ₄)(OH)；Na ₃KV ₂(SiO ₄) ₂(PO ₄)F；Na ₅TiFe(PO ₄) ₃F；

Na ₄K ₂VMg(PO ₄) ₃FCl；Na ₄NaAlNl(PO ₄) ₃(OH)；Na ₄K ₃FeMg(PO ₄) ₃F ₂；

Na ₄K ₂CrMn(PO ₄) ₃(OH)Br；Na ₅TiCa(PO ₄) ₃F；Na ₄Ti _0.75Fe _1.5(PO ₄) ₃F；

Na ₄SnFe(PO ₄) ₃(OH)；Na ₃NaGe _0.5Ni ₂(PO ₄) ₃(OH)；Na ₃K ₂VCo(PO ₄) ₃(OH)Cl；

Na ₄Na ₂MnCa(PO ₄) ₃F(OH)；Na ₄KTiFe(PO ₄) ₃F；Na ₇FeCo(SiO ₄) ₂(PO ₄)F；

Na ₆TiV(SiO ₄) ₂(PO ₄)F；K _5.5CrMn(SiO ₄) ₂(PO ₄)Cl _0.5；Na _5.5V ₂(SiO ₄) ₂(PO ₄)(OH) _0.5；

Na _5.25FeMn(SiO ₄) ₂(PO ₄)Br _0.25；Na _6.5VCo(SiO ₄) _2.5(PO ₄) _0.5F；

Na _7.25V ₂(SiO ₄) _2.25(PO ₄) _0.75F ₂；Na ₅VTi(SiO ₄) ₃F _0.5Cl _0.5；Na ₂K _2.5ZrV(SiO ₄) ₃F _0.5；

Na ₄K ₂MnV(SiO ₄) ₃(OH) ₂；Na ₃Na ₃KTi ₂(SiO ₄) ₃F；K ₆V ₂(SiO ₄) ₃(OH)Br；

Na ₈FeMn(SiO ₄) ₃F ₂；Na _7.5MnNi(SiO ₄) ₃(OH) _1.5；Na ₅K ₂TiV(SiO ₄) ₃(OH) _0.5Cl _0.5；

K ₉VCr(SiO ₄) ₃F ₂Cl；Na ₈V ₂(SiO ₄) ₃FBr；Na ₄FeMg(SO ₄) ₃F ₂；

Na ₂KNiCo(SO ₄) ₃(OH)；Na ₅MnCa(SO ₄) ₃F ₂Cl；Na ₄CoBa(SO ₄) ₃FBr；

Na _2.5K _0.5FeZn(SO ₄) ₃F；Na ₃MgFe(SO ₄) ₃F ₂；Na ₃CaV(SO ₄) ₃FCl；

Na ₄NiMn(SO ₄) ₃(OH) ₂；Na ₂KBaFe(SO ₄) ₃F；Na ₂KCuV(SO ₄) ₃(OH)Br；

Na _1.5CoPO ₄F _0.5；Na _1.25CoPO ₄F _0.25；Na _1.75FePO ₄F _0.75；Na _1.66MnPO ₄F _0.66；

Na _1.5Co _0.75Ca _0.25PO ₄F _0.5；Na _1.75Co _0.8Mn _0.2PO ₄F _0.75；Na _1.25Fe _0.75Mg _0.25PO ₄F _0.25；

Na _1.66Co _0.6Zn _0.4PO ₄F _0.66；KMn ₂SiO ₄Cl；Na ₂VSiO ₄(OH) ₂；Na ₃CoGeO ₄F；

NaMnSO ₄F；NaFe _0.9Mg _0.1SO ₄Cl；NaFeSO ₄F；NaMnSO ₄OH；KMnSO ₄F；

Na _1.75Mn _0.8Mg _0.2PO ₄F _0.75；Na ₃FeZn(PO ₄)F ₂；Na _0.5V _0.75Mg _0.5(PO ₄)F _0.75；

Na ₃V _0.5Al _0.5(PO ₄)F _3.5；Na _0.75VCa(PO ₄)F _1.75；Na ₄CuBa(PO) ₄)F ₄；

Na _0.5V _0.5Ca(PO ₄)(OH) _1.5；Na _1.5FeMg(PO ₄)(OH)Cl；NaFeCoCa(PO ₄)(OH) ₃F；

Na ₃CoBa(PO ₄)(OH) ₂Br ₂；Na _0.75Mn _1.5Al(PO ₄)(OH) _3.75；Na ₂Co _0.75Mg _0.25(PO ₄)F；

Na ₂Co _0.8Mg _0.2(PO ₄)F；NaKCo _0.5Mg _0.5(PO ₄)F；Na _1.5K _0.5Fe _0.75Mg _0.25(PO ₄)F；

Na _1.5K _0.5V _0.5Zn _0.5(PO ₄)F ₂；Na ₆Fe ₂Mg(PS ₄) ₃(OH ₂)Cl；

Na ₄Mn _1.5Co _0.5(PO ₃F) ₃(OH) _3.5；K ₈FeMg(PO ₃F) ₃F ₃Cl ₃Na ₅Fe ₂Mg(SO ₄) ₃Cl ₅；

NaTi ₂(SO ₄) ₃Cl，NaMn ₂(SO ₄) ₃F，Na ₃Ni ₂(SO ₄) ₃Cl，Na ₃Co ₂(SO ₄) ₃F，

Na ₃Fe ₂(SO ₄) ₃Br，Na ₃Mn ₂(SO ₄) ₃F，Na ₃MnFe(SO ₄) ₃F，Na ₃NiCo(SO ₄) ₃Cl；

NaMnSO ₄F；NaFeSO ₄Cl；NaNiSO ₄F；NaCoSO ₄Cl；NaMn _1-xFe _xSO ₄F，NaFe ₁.

_xMg _xSO ₄F；Na ₇ZrMn(SiO ₄) ₃F；Na ₇MnCo(SiO ₄) ₃F；Na ₇MnNi(SiO ₄) ₃F；

Na ₇VAl(SiO ₄) ₃F；Na ₅MnCo(PO ₄) ₂(SiO ₄)F；Na ₄VAl(PO ₄) ₂(SiO ₄)F；

Na ₄MnV(PO ₄) ₂(SiO ₄)F；Na ₄VFe(PO ₄) ₂(SiO ₄)F；Na _0.6VPO ₄F _0.6；Na _0.8VPO ₄F _0.8；

NaVPO ₄F；Na ₃V ₂(PO ₄) ₂F ₃；NaVPO ₄Cl；NaVPO ₄OH；NaVPO ₄F；

Na ₃V ₂(PO ₄) ₂F ₃；NaV _0.9Al _0.1PO ₄F；NaFePO ₄F；NaTiPO ₄F；NaCrPO ₄F；NaFePO ₄；

NaCoPO ₄，NaMnPO ₄；NaFe _0.9Mg _0.1PO ₄；NaFe _0.8Mg _0.2PO ₄；NaFe _0.95Mg _0.05PO ₄；

NaFe _0.9Ca _0.1PO ₄；NaFe _0.8Ca _0.2PO ₄；NaFe _0.8Zn _0.2PO ₄；NaMn _0.8Fe _0.2PO ₄；

NaMn _0.9Fe _0.8PO ₄；Na ₃V ₂(PO ₄) ₃；Na ₃Fe ₂(PO ₄) ₃；Na ₃Mn ₂(PO ₄) ₃；Na ₃FeTi(PO ₄) ₃；

Na ₃CoMn(PO ₄) ₃；Na ₃FeV(PO ₄) ₃；Na ₃VTi(PO ₄) ₃；Na ₃FeCr(PO ₄) ₃；

Na ₃FeMo(PO ₄) ₃；Na ₃FeNi(PO ₄) ₃；Na ₃FeMn(PO ₄) ₃；Na ₃FeAl(PO ₄) ₃；

Na ₃FeCo(PO ₄) ₃；Na ₃Ti ₂(PO ₄) ₃；Na ₃TiCr(PO ₄) ₃；Na ₃TiMn(PO ₄) ₃；Na ₃TiMo(PO ₄) ₃；

Na ₃TiCo(PO ₄) ₃；Na ₃TiAl(PO ₄) ₃；Na ₃TiNi(PO ₄) ₃；Na ₃ZrMnSiP ₂O ₁₂；Na ₃V ₂SiP ₂O ₁₂；

Na ₃MnVSiP ₂O ₁₂；?Na ₃TiVSiP ₂O ₁₂；Na ₃TiCrSiP ₂O ₁₂；Na _3.5AlVSi _0.5P _2.5O ₁₂；

Na _3.5V2Si _0.5P _2.5O ₁₂；Na _2.5AlCrSi _0.5P _2.5O ₁2；Na _2.5V ₂P ₃O _11.5F _0.5；Na ₂V ₂P ₃O ₁₁F；

Na _2.5VMnP ₃O _11.5F _0.5；Na ₂V _0.5Fe _1.5P ₃O ₁₁F；Na ₃V _0.5V _1.5P ₃O _11.5F _0.5；Na ₃V ₂P ₃O ₁₁F；

Na ₃Mn _0.5V _1.5P ₃O ₁₁F _0.5；NaCo _0.8Fe _0.1Ti _0.025Mg _0.05PO ₄；

Na _1.025Co _0.8Fe _0.1Ti _0.025Al _0.025PO ₄；Na _1.025Co _0.8Fe _0.1Ti _0.025Mg _0.025PO _3.975F _0.025；

NaCo _0.825Fe _0.1Ti _0.025Mg _0.025PO ₄；NaCo _0.85Fe _0.075Ti _0.025Mg _0.025PO ₄；

NaCo _0.8Fe _0.1Ti _0.025Al _0.025Mg _0.025PO ₄.Na _1.025Co _0.8Fe _0.1Ti _0.025Mg _0.05PO ₄，

Na _1.025Co _0.8Fe _0.1Ti _0.025Al _0.025Mg _0.025PO ₄，NaCo _0.8Fe _0.1Ti _0.05Mg _0.05PO ₄，

With and the lithium analog.

The preferred active material of this Asia execution mode comprises:

NaFePO ₄；NaCoPO ₄，NaMnPO ₄；NaMn _0.8Fe _0.2PO ₄；NaMn _0.9Fe _0.9PO ₄；

NaFe _0.9Mg _0.1PO ₄；NaFe _0.8Mg _0.2PO ₄；NaFe _0.95Mg _0.05PO ₄；

Na _1.025Co _0.85Fe _0.05Al _0.025Mg _0.05PO ₄，Na _1.025Co _0.80Fe _0.10Al _0.025Mg _0.05PO ₄，

Na _1.025Co _0.75Fe _0.15Al _0.025Mg _0.05PO ₄，Na _1.025Co _0.7(Fe _0.4Mn _0.6) _0.2Al _0.025Mg _0.05PO ₄，

NaCo _0.8Fe _0.1Al _0.025Ca _0.025PO _3.975F _0.025，NaCo _0.8Fe _0.1Al _0.025Mg _0.05PO _3.975F _0.025，

NaCo _0.8Fe _0.1Ti _0.025Mg _0.05PO ₄；Na _1.025Co _0.8Fe _0.1Ti _0.025Al _0.025PO ₄；

Na _1.025Co _0.8Fe _0.1Ti _0.025Mg _0.025PO _3.975F _0.025；NaCo _0.825Fe _0.1Ti _0.025Mg _0.025Po ₄；

NaCo _0.85Fe _0.075Ti _0.025Mg _0.025PO ₄。Particularly preferred active material is NaFePO ₄And Na ₃V ₂(PO ₄) ₃

In a concrete inferior execution mode, cathode film 26 contains the electrode active material by following general formula (III) expression:

A _aM _bO _e， (III)

Wherein:

(i) component A and M as mentioned above, 0＜a≤6 and 1≤b≤6 wherein; And

(ii)0＜e≤15；

Wherein, select M, a, b and e, make the electric neutrality of keeping nascent state or synthetic attitude material.

Preferred 2≤e≤13, and more preferably 2≤e≤8.

The preferred electrode active material of this inferior execution mode comprises the compound of formula (IV):

A _aNi _tCo _uM ⁴ _vO ₂， (IV)

Wherein 0＜(t+u)≤1, and 0≤t＜1.In one embodiment, t=(1-u), wherein t=0.In another embodiment, t=(1-u-v), wherein v＞0.M ⁴Be at least a metal that is selected from periodic table the 2nd family, the 12nd family, the 13rd family or the 14th family, more preferably M ⁴Be selected from the group of following composition: Mg, Ca, Al and composition thereof.

The preparation as general formula (III) and the method for the electrode active material (IV) know in the art, and description is arranged in following patent documentation: the United States Patent (USP) 5 of signing and issuing people such as Garcia-Alvarado on July 6th, 1993,225,297, signed and issued people's such as Koksbang United States Patent (USP) 5 on August 23rd, 1994,340,671, signed and issued people's such as Koksbang United States Patent (USP) 5 on November 22nd, 1994,366,830, signed and issued people's such as Amatucci United States Patent (USP) 5 on December 24th, 1996,587,133, signed and issued people's such as Amatucci United States Patent (USP) 5,630,993 on May 20th, 1997, signed and issued people's such as Barker United States Patent (USP) 5 on September 23rd, 1997,670,277, signed and issued people's such as Amatucci United States Patent (USP) 5,693,435 on December 2nd, 1997, signed and issued people's such as Barker United States Patent (USP) 5 on December 16th, 1997,698, signed and issued people's such as Barker United States Patent (USP) 5,744,265 on April 28th, 338 and 1998.

In this Asia execution mode by general formula (I), (III) and (IV) non-limiting example of the active material of expression comprise following cited:

NaMn ₂O ₄，NaNi _0.75Al _0.25O ₂，Na ₂CuO ₂，Y-NaV ₂O ₅，LiCo _0.5Ni _0.5O ₂，NaCoO ₂，

NaNiO ₂，NaNiCoO ₂，NaNi _0.75Co _0.25O ₂，NaNi _0.8Co _0.2O ₂，NaNi _0.6Co _0.4O ₂，NaMnO ₂，

NaMoO ₂，NaNi _0.8Co _0.15Al _0.05O ₂，NaFeO ₃，α-NaFe ₅O ₈，β-NaFe ₅O ₈，Na ₂Fe ₃O ₄，

NaFe ₂O ₃，NaM _0.6Co _0.2Al _0.2O ₂，NaNi _0.8Co _0.15Mg _0.05O ₂，NaNi _0.8Co _0.15Ca _0.05O ₂，

NaNi _0.8Co _0.15Al _0.05O ₂，NaCr _0.8Co _0.15Al _0.05O ₂，Na _0.5Na _0.5CoO ₂，NaNi _0.6Co _0.4O ₂，

KNi _0.75Co _0.25O ₂，NaFe _0.75Co _0.25O ₂，NaCu _0.8Co _0.2O ₂，NaTi _0.9Ni _0.1O ₂，

NaV _0.8Co _0.2O2，Na ₃V ₂Co _0.5Al _0.5O ₅，Na ₂NaVNi _0.5Mg _0.5O ₅，Na ₅CrFe _1.5CaO ₇，

NaCrO ₂，NaVO ₂，NaTiO ₂，NaVO ₂，NaTiO ₂，Na ₂FeV ₂O ₅，Na ₅Ni _2.5Co ₃O ₈；

Na ₆V ₂Fe _1.5CaO ₉, its potassium (K) analog and lithium (Li) analog, and their mixture.Preferable material comprises NaNiO ₂, NaCoO ₂, NaNi _1-xCo _xO ₂, γ-NaV ₂O ₅And Na ₂CuO ₂

In a concrete inferior execution mode, cathode film 26 contains the electrode active material by following general formula (V) expression:

A _aMn _bO ₄， (V)

(this paper " Mn oxide of modification "), it has interior zone and perimeter, and wherein interior zone comprises a kind of cubic spinel Mn oxide, and the perimeter is with respect to interior zone enrichment Mn ^{+ 4}, component A and selects a and b to keep the electric neutrality of nascent state or synthetic attitude material as mentioned above.

Preferred 0＜a≤2.0, more preferably 0.8≤a≤1.5, and more preferably 0.8≤a≤1.2.

In a preferred implementation, the Mn oxide active material of this modification is characterised in that particle has the core or the bulk structure (bulk structure) of cubic spinel Mn oxide, and for body phase (bulk) enrichment Mn ²⁺Surf zone.X-ray diffraction data and x-ray photoelectron spectroscopy are learned data and are consistent with stable Mn oxide structure, are shown as superficial layer or surf zone comprises A ₂MnO ₃The centerbody (central bulk) of cubic spinel Mn oxide, wherein A is an alkali metal.

Mixture preferably contains and is less than 50wt%, preferably is less than the alkali metal compound of about 20wt%.Mixture contains at least about 0.1wt%, preferred 1wt% or more alkali metal compound.One preferred embodiment in, mixture contains the 0.1wt% that has an appointment～about 20wt%, preferred 0.1wt%～about 10wt%, and the more preferably alkali metal compound of 0.4wt%～about 6wt%.

Alkali metal compound is the compound of lithium, sodium, potassium, rubidium or caesium.Alkali metal compound is as the alkali metal ion source of particle form.Preferred alkali metal compound is sodium compound and lithium compound.Examples for compounds includes but not limited to carbonate, metal oxide, hydroxide, sulfate, aluminate, phosphate and silicate.Therefore the example of lithium compound includes but not limited to lithium carbonate, lithium metal oxide, lithium mixed-metal oxides, lithium hydroxide, lithium aluminate and lithium metasilicate, and similarly sodium compound also is preferred simultaneously.Preferred lithium compound is a lithium carbonate.Sodium carbonate and NaOH are preferred sodium compounds.The Mn oxide preferable feature of modification is that it is compared with the spinel lithium-manganese oxide that does not have modification and has reduced surface area and increased alkali metal content.In another was selected, all lithium compounds or sodium compound were decomposed or react with lithium manganese oxide basically.

In one aspect, catabolite is the product of LMO particle and alkali metal compound.When alkali metal is lithium, preferably be rich in the spinelle of lithium.The execution mode of preferred electrode active material comprises that formula is A _1+pMn _2-pO ₄Compound, 0≤p＜0.2 wherein.Preferred p is more than or equal to about 0.081.

In many execution modes, the Mn oxide material of modification of the present invention is red.Be not subject to theory, this redness may be by the Li that is positioned at surface or crystal boundary ₂MnO ₃(or Na ₂MnO ₃, it also is red) deposition or nucleation caused.Be not subject to theory, a method of the Mn oxide of this redness modification of imagination formation is as follows.Mn on cubic spinel lithiumation manganese oxide particle surface ^{+ 3}Lose an electronics, make it be able to combine with alkali metal in the alkali metal compound that adds.Preferably, alkali metal compound is a lithium carbonate.Therefore, this cubic spinel lithiumation Mn oxide enriching lithium that becomes.In the solid-state building-up process by with atmosphere (air) in combination with oxygen keep charge balance.Particle surface Mn ^{+ 3}Be oxidized to Mn ^{+ 4}Cause capacitance loss and structure cell to shrink.Therefore, the surf zone of particle is at cubic spinel lithiumation Mn oxide and the lithium compound relative Mn that increased in the course of reaction in air or in the presence of oxygen ^{+ 4}Form.At least in initial reaction stage, form Li at particle surface ₂MnO ₃Superficial layer or coating.Therefore think the Li of the formed redness of particle surface ₂MnO ₃(Na ₂MnO ₃) cause in some samples of the treated LMO of the present invention, observing redness.

The method of the electrode active material of preparation shown in general formula (V) is known in the art, and description is arranged in following patent documentation: the United States Patent (USP) 5 of signing and issuing people such as Barker on February 9th, 1999,869,207, sign and issue people's such as Barker United States Patent (USP) 6 February 6 calendar year 2001, signed and issued people's such as Barker United States Patent (USP) 6,869 on March 22nd, 183,718,2005, signed and issued people's such as Barker United States Patent (USP) 5.596,435 on July 22nd, 547 and 2003.

In a concrete inferior execution mode, cathode film 26 contains the electrode active material by following general formula (VI) expression:

A _a(M′O) _cXO ₄Z _f， (VI)

Wherein:

(i) component A, M ' and Z as mentioned above, wherein 0＜a≤9,0＜c≤1 and 0≤f≤4; And

(ii) X is selected from the group of following composition: P, As, Sb, Si, Ge, V, S and composition thereof;

Wherein, select A, M ', X, a, c and f, make the electric neutrality of keeping nascent state or synthetic attitude material.

In a concrete inferior execution mode, (M ' O) is the 2+ valency ion that contains 4+ valency metal to the component of general formula (VI).Preferred M ' is vanadium (V), and XY ₄=PO ₄

The method of the electrode active material of preparation shown in general formula (VI) is known in the art, and in following patent documentation description is arranged: people's such as announcement on December 30th, 2004 Barker U.S.Publication No.2002/0262571.

In this Asia execution mode by general formula (I) and (VI) non-limiting example of active material of expression comprise following cited:

NaVOPO ₄, Na (VO) _0.75Mn _0.25PO ₄, NaVOPO ₄, NaVOPO ₄, Na (VO) _0.5Al _0.5PO ₄, Na (VO) _0.75Fe _0.25PO ₄, Na _0.5Na _0.5VOPO ₄, Na (VO) _0.75Co _0.25PO ₄, Na (VO) _0.75Mo _0.25PO ₄And NaVOSO ₄Particularly preferably be NaVOPO ₄And Na (VO) _0.75Mn _0.25PO ₄

In a concrete inferior execution mode, cathode film 26 contains the electrode active material by following general formula (VII) expression:

A _aM _bWO ₄， (VII)

Wherein:

(i) component A and M as mentioned above, 0＜a≤2 and 0＜b≤1 wherein; And

(ii) W is selected from the group of following composition: Hf, Ti, Zr and composition thereof;

Wherein, select A, M, W, a and b, to keep the electric neutrality of nascent state or synthetic attitude material.

In a concrete inferior execution mode, component M is selected from the group of following composition: Ni, Co, Fe, Mn, V, Cr and composition thereof.

The method of the electrode active material shown in preparation general formula (VI) is known in the art, and in following patent documentation description is arranged: the United States Patent (USP) 6,103,419 of signing and issuing people such as Saidi on August 15th, 2000.

In this Asia execution mode by general formula (I) and (VII) non-limiting example of active material of expression comprise following cited:

Na ₂FeTiO ₄, Na ₂FeZrO ₄, Na ₂VTiO ₄, Na ₂VZrO ₄, Na ₂NiTiO ₄And Na ₂NiZrO ₄

Following non-limiting example illustrates composition of the present invention and method.

Embodiment 1

Formula is Na _1.025Co _0.9Al _0.025Mg _0.05PO ₄Electrode active material be prepared as follows.Following Li, the Co, Al, Mg and the PO that are provided ₄The source, the mol ratio that contains each element is 1.025: 0.9: 0.025: 0.05: 1.

0.05125 mole Na ₂CO ₃(molecular weight is 105.99g/mol) 7.7g

0.03 mole Co ₃O ₄(240.8g/mol) 7.2g

0.0025 mole Al (OH) ₃(78g/mol) 0.195g

0.005 mole Mg (OH) ₂(58g/mol) 0.29g

0.1 mole (NH ₄) ₂HPO ₄(132g/mol) 13.2g

0.2 mole simple substance carbon (12g/mol) (＞100% is excessive) 2.4g

With above initiation material in conjunction with and carry out ball milling with hybrid particles.Thereafter, granulate mixture is made granular.Under argon atmospher, in 750 ℃ baking oven, heated this particulate mixtures 4 to 20 hours.Then, from baking oven, shift out this sample, make its cooling.X-ray diffraction pattern shows that this material has the olivine-type crystal structure.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode (carbon intercalation anode) with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, the 1M LiPF in mixture w/w) ₆

Embodiment 2

Formula is Na _1.025Co _0.8Fe _0.1Al _0.025Mg _0.05PO ₄Electrode active material be prepared as follows.Following Na, the Co, Fe, Al, Mg and the PO that are provided ₄The source, the mol ratio that contains each element is 1.025: 0.8: 0.1: 0.025: 0.05: 1.

0.05125 mole Na ₂CO ₃(molecular weight is 105.99g/mol) 7.7g

0.02667 mole Co ₃O ₄(240.8g/mol) 6.42g

0.005 mole Fe ₂O ₃(159.7g/mol) 0.8g

0.0025 mole Al (OH) ₃(78g/mol) 0.195g

0.005 mole Mg (OH) ₂(58g/mol) 0.29g

0.1 mole (NH ₄) ₂HPO ₄(132g/mol) 13.2g

0.2 mole simple substance carbon (12g/mol) (＞100% is excessive) 2.4g

With above initiation material in conjunction with and carry out ball milling with hybrid particles.Thereafter, granulate mixture is made granular.Under argon atmospher, in 750 ℃ baking oven, heated this particulate mixtures 4 to 20 hours.Then, from baking oven, shift out this sample, make its cooling.X-ray diffraction pattern shows that this material has the olivine-type crystal structure.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in gamma-butyrolacton: and ethylene carbonate (3: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 3

Contain Na ₂NiPO ₄F (formula Na _1+xNiPO ₄F _xRepresentative) electrode active material be prepared as follows.At first, prepare NaNiPO according to following reaction path ₄Precursor.

0.5Na ₂CO ₃+0.334Ni ₃(PO ₄) ₂.7H ₂O+0.334(NH ₄) ₂HPO ₄→

LiNiPO ₄+2.833?H ₂O+0.667NH ₃+0.5CO ₂

Make 52.995g (0.5mol) Na with mortar and pestle ₂CO ₃, 164.01g (0.334mol) Ni ₃(PO ₄) ₂.7H ₂O and 44.11g (0.334mol) (NH ₄) ₂HPO ₄Mixture.Mixture is made granular, and transferred in the baker that has disposed big entraining air stream.Heating rate with 2 ℃ of per minutes is heated to about 800 ℃ final temperature with this mixture, and keeps this temperature 16 hours.Then, product is cooled to room temperature (about 21 ℃).

Then by NaNiPO ₄Precursor makes Na _1+xNiPO ₄F _xIn following embodiment, x is 1.0, thereby active material is by formula Na ₂NiPO ₄F represents.Prepare this material according to following reaction path.

NaNiPO ₄+xNaF→Na _1+xNiPO ₄F _x

Equal 1.0 for x, make 1mol LiNiPO with mortar and pestle ₄Mixture with 1mol NaF.Mixture is made granular, and transferred in the temperature control tube furnace that has disposed argon stream.Heating rate with 2 ℃ of per minutes is heated to about 850 ℃ final temperature with this mixture.Then, product is cooled to room temperature (about 20 ℃).Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in gamma-butyrolacton: and ethylene carbonate (3: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 4

Contain Na _1.2VPO ₄F _1.2Electrode active material be prepared as follows.In the first step, the carbon thermal reduction by metal oxide (at this with vanadic oxide as an example) prepares metal phosphate.The overall reaction approach of carbon thermal reduction is as follows.

0.5V ₂O ₅+NH ₄H ₂PO ₄+C→VPO ₄+NH ₃+1.5H ₂O+CO

Use 9.1g V ₂O ₅, 11.5g NH ₄H ₂PO ₄And 1.2g (10% is excessive) carbon.With the precursor premixed, and be made into granular with mortar and pestle.This shot-like particle is transferred in the baking oven that has disposed argon stream.Heating rate with 2 ℃ of per minutes is heated to 300 ℃ final temperature with this sample, and keeps this temperature 3 hours.Cool off this sample then, and it is shifted out, reclaim, mix again and granulate again from baking oven.This shot-like particle is transferred in the smelting furnace under the argon atmospher.Heating rate with 2 ℃ of per minutes is heated to 750 ℃ final temperature with this sample, and keeps this temperature 8 hours.

In second step, phosphoric acid vanadium and the alkali halide (with sodium fluoride as an example) that the first step makes reacted according to following reaction path.

xNaF+VPO ₄→Na _xVPO ₄F _x

Use 14.6g VPO ₄With 4.2g NaF.With the precursor premixed, and be made into granular with mortar and pestle.This shot-like particle is transferred in the baking oven that has disposed argon stream.Heating rate with 2 ℃ of per minutes is heated to 750 ℃ final temperature with this sample, and keeps this temperature 1 hour.Cool off this sample then, and it is shifted out from baking oven.

In order to prepare Na _1.2VPO ₄F _1.2, with exceeding the excess of fluoride reaction repeated of above-mentioned reaction 20%.The same, use mortar and pestle with the precursor premixed, and be made into granular.Sample is heated to 700 ℃ final temperature, and kept this temperature 15 minutes.Cool off this sample then, and it is shifted out from baking oven.In course of reaction, a spot of loss in weight is only arranged, expression NaF almost completely incorporates into.For preparation formula is Na _1.5VPO ₄F _1.5Active material, with exceeding the excess of fluoride reaction repeated of first set reaction about 50%.This sample of heating is 15 minutes under 700 ℃ temperature.Cool off this sample then, and it is shifted out from baking oven.

Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 5

Contain NaCoPO according to following reaction path preparation ₄The electrode active material of F.

0.33Co ₃O ₄₊NH ₄H ₂PO ₄+NaF+0.083O ₂→NaCoPO ₄F+NH ₃+1.5H ₂O

This active material of preparation under oxidation environment, wherein the oxidation state of the metal in the end product is higher than the oxidation state of the metal in the initiation material.With 3gCo ₃O ₄, 1.57gNaF and 4.31g NH ₄H ₂PO ₄Mix, make granularly, and be heated to 300 ℃ final temperature, and kept this temperature 3 hours.Cool off this sample then, and it is shifted out, granulate again, and send baking oven again back to, be heated to 800 ℃ final temperature, and kept this temperature 8 hours from baking oven.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 6

Contain Li according to following reaction path preparation _0.1Na _0.9VPO ₄The electrode active material of F.

xLiF+(1-x)NaF+VPO ₄→Li _xNa _1-xVPO ₄F

As another selection of alkali metal fluoride, can use VPO ₄And NH ₄Reaction between the F and Li ₂CO ₃And Na ₂CO ₃Mixture.

In order to prepare Li _0.1Na _0.9VPO ₄F is with 1.459g VPO ₄, 0.026g LiF and 0.378g NaF premixed, make granularly, and be positioned over baking oven and be heated to 700 ℃ final temperature.Keeping this temperature 50 minutes, thereafter this sample is cooled to room temperature, and shifts out from baking oven.In order to prepare Li _0.95Na _0.05VPO ₄F is with 1.459g VPO ₄, 0.246g LiF and 0.021g NaF mix, then as before step in baking oven, be heated.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 7

Prepare in the hydro-thermal mode according to following reaction path and to contain NaVPO ₄The electrode active material of F.

NaF+VPO ₄→NaVPO ₄F

With 1.49g VPO ₄With 1.42g NaF and about 20 milliliters deionized water premixed, with its transfer and be sealed in the Parr Model 4744 acid digestion bullets (acid digestion bomb), it is the stainless steel hydrothermal reaction kettle of Teflon inner bag.Should acid the digestion bullet be placed in the baking oven, and this sample is heated to 250 ℃ final temperature with the heating rate of 5 ℃ of per minutes, forming interior pressure, and under this temperature, kept 48 hours.Then this sample is cooled to room temperature at leisure, and it is shifted out to analyze from baking oven.Repeat with this product sample of deionized water rinsing to remove unreacted impurity.In the baking oven that has disposed argon stream 250 ℃ dry one hour then.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 8

Contain NaVPO according to following another optional reaction path preparation ₄The electrode active material of OH.

NaOH+VPO ₄→NaVPO ₄OH

In this embodiment, repeat the reaction of embodiment 14, the different NaOH that are to use suitable mole replace sodium fluoride.As embodiment 14, carry out this reaction in the hydro-thermal mode.Under the reaction of relatively lower temp, hydroxyl is incorporated in the active material.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 9

Contain NaVPO according to following reaction path preparation ₄The electrode active material of F.

0.5Na ₂CO ₃+NH ₄F+VPO ₄→NaVPO ₄F+NH ₃+0.5CO ₂+0.5H ₃O

With 1.23g VPO ₄, 0.31g NH ₄F and 0.45g Na ₂CO ₃With about 20 milliliters deionized water premixed, with its transfer and be sealed in the Parr Model 4744 acid digestion bullets, it is the stainless steel hydrothermal reaction kettle of Teflon inner bag.Should be placed in the baking oven by acid digestion bullet, and this sample is heated to 250 ℃ final temperature, and under this temperature, kept 48 hours with the heating rate of 5 ℃ of per minutes.Then this sample is cooled to room temperature, and it is shifted out to analyze from baking oven.Repeat with this sample of deionized water rinsing to remove unreacted impurity under argon atmospher in 250 ℃ the baking oven dry one hour thereafter.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 10

Contain Li according to following reaction path preparation ₄Fe ₂(PO ₄) ₃F (general formula A _aM _b(PO ₄) ₃Z _dRepresentative) electrode active material.

2Li ₂CO ₃+Fe ₂O ₃+3NH ₄H ₂(PO ₄)+NH ₄F→Li ₄Fe ₂(PO ₄) ₃F+2CO ₂+4NH ₃+

5H ₂O

At this, M ₂O ₃Expression+3 valent metal oxides or+mixture of 3 valent metal oxides.Can use the lithium carbonate, sodium carbonate and the potassium carbonate mixtures that are total up to 2 moles to replace the preparation of 2 lithium carbonates to have lithium, sodium and potassium as alkali-metal similar compound.Parent material carbonic acid alkali metal, metal or hybrid metal+oxide, ammonium dihydrogen phosphate and the ammonium fluoride of 3 valency oxidation state be mixed into powder by the stoichiometric proportion of appointment, and embodiment as described above, with powder and make granular.This shot-like particle is transferred in the baking oven, and be heated to about 800 ℃ final temperature, and kept this temperature 8 hours.Cool off this reactant mixture then, and it is shifted out from baking oven.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 11

Contain Na according to following reaction path preparation ₂Li ₂M ₂(PO ₄) ₃Electrode active material.

Li ₂CO ₃+Na ₂CO ₃+2MPO ₄+NH ₄H ₂PO ₄+NH ₄F→

Na ₂Li ₂M ₂(PO ₄) ₃F+2CO ₂+2NH ₃+2H ₂O

According to the general procedure of embodiment 10, parent material is mixed by the stoichiometric proportion of appointment and react.At this, MPO ₄The expression+3 valency metal phosphates or+3 valency metal tripolyphosphate salt mixtures.Make the electrode that contains 80% active material, 10%Super P conductive carbon and 10% polyvinylidene fluoride.Insert anode with this electrode as negative electrode and carbon, constituted battery with electrolyte, described electrolyte comprises and is dissolved in ethylene carbonate: and dimethyl carbonate (2: 1, w/w) the 1M LiPF in the mixture ₆

Embodiment 12

Contain Na ₃V ₂(PO ₄) ₂F ₃Electrode active material be prepared as follows.At first, prepare VPO according to following reaction path ₄Precursor.

V ₂O ₅+2(NH ₄) ₂HPO ₄+C→VPO ₄

Make 18.2g (0.1mol) V with mortar and pestle ₂O ₅, 26.4g (0.2mol) (NH ₄) ₂HPO ₄And the mixture of 2.4g (0.2mol) simple substance carbon.Mixture is made granular, and transferred in the baker that has disposed argon stream.This mixture is heated to about 350 ℃, and kept this temperature 3 hours.Then, this mixture is heated to about 750 ℃, and kept this temperature 8 hours.Then, it is cooled to room temperature (about 21 ℃).

Then by VPO ₄Precursor makes Na ₃V ₂(PO ₄) ₂F ₃Prepare this material according to following reaction path.

2VPO ₄+3NaF→Na ₃V ₂(PO ₄) ₂F ₃

Make 2mol VPO with mortar and pestle ₄Mixture with 3mol NaF.Mixture is made granular, and transferred in the temperature control tube furnace that has disposed argon stream.Heating rate with 2 ℃ of per minutes heats 1 hour to about 750 ℃ final temperature with this mixture.Then, product is cooled to room temperature (about 20 ℃).To Na ₃V ₂(PO ₄) ₂F ₃It is single-phase tetragonal (space group P4 that the X-ray powder diffraction analysis of material demonstrates this material ₂/ mnm).Calculate cell parameter by the least square refinement program

, people such as itself and Meins is at J.Solid State Chem.148,260, in (1999) to Na ₃V ₂(PO ₄) ₂F ₃Structural analysis conform to (that is, ).

Make the electrode that contains 84% active material, 5%Super P conductive carbon and 11-wt%PVdF-HFP copolymer (ElfAtomchem) binding agent.Electrolyte comprises and contains 1M LiPF ₆Ethylene carbonate/dimethyl carbonate (2: 1, w/w) solution, the glass fiber filter paper of use doing (Whatman, Grade GF/A) is as the electrode isolation thing.Use commercially available kish as active material of positive electrode.(Electrochemical Voltage Spectroscopy, EVS) technology is carried out the high accuracy electrochemical measurement to utilize electrochemical voltage spectroscopy.EVS is a kind of voltage step method (voltage step method), and its open circuit voltage curve for the electro-chemical systems just studied provides high accuracy to approach.This technology is known in this area, and at J.Barker in Synth.Met 28, D217 (1989); Synth.Met 32,43 (1989); J Power Sources, 52,185 (1994); With Electrochemica Acta, Vol, 40, No.11, at 1603 (1995) has explanation.

Fig. 2 and Fig. 3 show graphite/1M LiPF ₆(EC/DMC)/Na ₃V ₂(PO ₄) ₂F ₃The voltage profile and the differential capacitance point diagram of rocking chair battery first circulation EVS response.In this structure, only Li is from LiPF in the system ₆The electrolyte phase of base.With respect to the negative electrode restriction system, used electrolytical actual volume is carefully controlled, and makes the charging of graphite active material is reached the operating limit that is about 300 mAh/g, or reaches Li _0.81C ₆

Fig. 4 shows representational graphite/Na ₃V ₂(PO ₄) ₂F ₃The circulation behavior of battery.Under the charge/discharge rates that is about C/2 and 2C, collect data.Initial negative electrode reversible capacity is in the scope of 115～120 mAh/g, and the circular list of battery reveals low relatively capacity attenuation behavior.A small amount of speed (rate) characteristic that shows this system's excellence that reduces of the discharge capacity that under two discharge rates, is write down.

Embodiment as herein described and other execution mode all are to be used to illustrate, and are not the scope that is used to limit the compositions and methods of the invention.Have in essence similar effect embodiment, material, composition and method equivalence variation, improvement and modification all within the scope of the present invention.

Claims (53)

1. electrochemical cell, it comprises:

First electrode, it comprises the electrode active material that contains at least a electrode active material charge carrier;

Second electrode; With

Electrolyte, it comprises at least a electrolyte charge carrier;

Wherein, in the nascent state of electrochemical cell, described at least a electrolyte charge carrier is different with described at least a electrode active material charge carrier.

2. the described electrochemical cell of claim 1, wherein said second electrode comprises the insertion active material.

3. the described electrochemical cell of claim 1, wherein said electrode active material comprises a kind of electrode active material charge carrier, and described electrolyte comprises a kind of electrolyte charge carrier, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is different with described electrode active material charge carrier.

4. the described electrochemical cell of claim 3, wherein in the nascent state of described electrochemical cell, described electrode active material charge carrier is selected from the group that is made of periodic table I family and II family element and composition thereof.

5. the described electrochemical cell of claim 4, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is a lithium.

6. the described electrochemical cell of claim 1, wherein in the nascent state of described electrochemical cell, described electrode active material is represented by following general formula:

A _aM _b(M′O) _c(XY ₄) _dO _eZ _f；

Wherein:

(i) A contains described at least a electrode active material, and 0＜a≤9;

(ii) M and M ' comprise at least a redox active element, and 1≤b≤6 and 0≤c≤;

(iii) XY ₄Be selected from [O by X ' _4-x, Y ' _x], X ' [O _4-y, Y ' _2y], X " S ₄, [X _z, X ' _1-z] O ₄, WO ₄

And composition thereof the group formed, wherein:

(a) X ' and X  independently are selected from the group of being made up of P, As, Sb, Si, Ge, V, S and composition thereof separately;

(b) X " is selected from the group of being made up of P, As, Sb, Si, Ge, V and composition thereof;

(c) W is selected from the group of being made up of V, Hf, Zr, Ti and composition thereof;

(d) Y ' is selected from the group of being made up of halogen, S, N and composition thereof, and wherein halogen is selected from periodic table the 17th family; And

(e) 0≤x≤3,0≤y≤2,0≤z≤1 and 0≤d≤3;

(iv) O is an oxygen, and 0≤e≤15, wherein when e＞0, (c, d)=0, wherein when d＞0, e=0; And

(v) Z is selected from the group of being made up of hydroxyl (OH), the halogen that is selected from periodic table the 17th family, nitrogen (N) and their mixture, and 0≤f≤4;

Wherein, select A, M, M ', X, Y, Z, a, b, c, x, y, z, d, e and f to keep the electric neutrality of nascent state electrode active material.

7. the described electrochemical cell of claim 6, wherein in the nascent state of described electrochemical cell, described A is selected from the group that is made of periodic table I family and II family element and composition thereof.

8. the described electrochemical cell of claim 6, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is a lithium.

9. the described electrochemical cell of claim 8, wherein in the nascent state of described electrochemical cell, described A is a sodium.

10. the described electrochemical cell of claim 6, wherein said M and M ' independently are selected from the group of being made up of the element of 11 families of periodic table the 4th family to the separately.

11. the described electrochemical cell of claim 6, at least one among wherein said M and the M ' is MI _nMII _o, wherein 0＜o+n≤b, and o and n all greater than zero (0＜o, n), wherein MI and MII each independently be selected from the group of forming by redox active element and non-oxide reducing activity element, wherein MI and MII at least one have redox active.

12. the described electrochemical cell of claim 6, wherein in the nascent state of described electrochemical cell, described electrode active material is represented by following general formula:

A _aM _b(XY ₄) _dZ _f，

1≤b≤3 wherein, and wherein select A, M, X, Y, Z, a, b, x, y, z, d and f to keep the electric neutrality of nascent state electrode active material.

13. the described electrochemical cell of claim 12, wherein in the nascent state of described electrochemical cell, described A is selected from the group that is made of periodic table I family and II family element and composition thereof.

14. the described electrochemical cell of claim 12, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is a lithium.

15. the described electrochemical cell of claim 14, wherein said electrolyte comprises the lithium salts of the group that is selected from following composition: LiClO ₄LiBF ₄LiPF ₆LiAlCl ₄LiSbF ₆LiSCN; LiCF ₃SO ₃LiCF ₃CO ₂Li (CF ₃SO ₂) ₂LiAsF ₆LiN (CF ₃SO ₂) ₂LiB ₁₀Cl ₁₀Lower aliphatic carboxylic acid lithium; LiCl; LiBr; LiI; Chlorine boron lithium; The tetraphenyl borate lithium; Imide li; And their mixture.

16. the described electrochemical cell of claim 14, wherein in the nascent state of described electrochemical cell, described A is a sodium.

17. the described electrochemical cell of claim 12, wherein said M is selected from by Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof the group formed, and XY ₄=PO ₄D=3, and f=0.

18. the described electrochemical cell of claim 12, wherein said M is selected from by Ti ²⁺, V ²⁺, Cr ²⁺, Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Mo ²⁺, Si ²⁺, Sn ²⁺, Pb ²⁺And composition thereof the group formed, and XY ₄=PO ₄D=1, and f=0.

19. the described electrochemical cell of claim 12, wherein said M is selected from by Ti ³⁺, V ³⁺, Cr ³⁺, Mn ³⁺, Fe ³⁺, Co ³⁺, Ni ³⁺, Mo ³⁺, Nb ³⁺And composition thereof the group formed, and XY ₄=PO ₄D=2.

20. the described electrochemical cell of claim 12, wherein said second electrode comprises the insertion active material, and it is selected from the group of being made up of transition metal oxide, metal chalcogenide, carbon and their mixture.

21. the described electrochemical cell of claim 20, wherein said insertion active material is a graphite.

22. the described electrochemical cell of claim 6, wherein in the nascent state of described electrochemical cell, described electrode active material is represented by following general formula:

A _aM _bO _e，

Wherein 0＜a≤6,1≤b≤6 and 0＜e≤15; And wherein select A, M, a, b and e, with the electric neutrality of the electrode active material of keeping nascent state.

23. the described electrochemical cell of claim 22, wherein in the nascent state of described electrochemical cell, described electrode active material is represented by following general formula:

A _aNi _tCo _uM ⁴ _vO ₂，

Wherein 0＜(t+u)≤1, and 0≤t＜1, and M ⁴Be at least a metal that is selected from periodic table the 2nd family, the 12nd family, the 13rd family or the 14th family, and wherein select A, M, a, t, u and v, with the electric neutrality of the electrode active material of keeping nascent state.

24. the described electrochemical cell of claim 22, wherein in the nascent state of described electrochemical cell, described A is selected from the group that is made of periodic table I family and II family element and composition thereof.

25. the described electrochemical cell of claim 22, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is a lithium.

26. the described electrochemical cell of claim 25, wherein said electrolyte comprises the lithium salts of the group that is selected from following composition: LiClO ₄LiBF ₄LiPF ₆LiAlCl ₄LiSbF ₆LiSCN; LiCF ₃SO ₃LiCF ₃CO ₂Li (CF ₃SO ₂) ₂LiAsF ₆LiN (CF ₃SO ₂) ₂LiB ₁₀Cl ₁₀Lower aliphatic carboxylic acid lithium; LiCl; LiBr; LiI; Chlorine boron lithium; The tetraphenyl borate lithium; Imide li; And their mixture.

27. the described electrochemical cell of claim 25, wherein in the nascent state of described electrochemical cell, described A is a sodium.

28. the described electrochemical cell of claim 22, wherein said second electrode comprises the insertion active material, and it is selected from the group of being made up of transition metal oxide, metal chalcogenide, carbon and their mixture.

29. the described electrochemical cell of claim 28, wherein said insertion active material is a graphite.

30. the described electrochemical cell of claim 6, wherein in the nascent state of described electrochemical cell, described electrode active material is represented by following general formula:

A _aMn _bO ₄，

It is characterized in that it has interior zone and perimeter, wherein interior zone comprises a kind of cubic spinel Mn oxide, and the perimeter is with respect to interior zone enrichment Mn ^{+ 4}, 0＜a≤2.0, and select A, a and b electric neutrality with the electrode active material of keeping nascent state.

31. the described electrochemical cell of claim 30, wherein in the nascent state of described electrochemical cell, described A is selected from the group that is made of periodic table I family and II family element and composition thereof.

32. the described electrochemical cell of claim 30, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is a lithium.

33. the described electrochemical cell of claim 32, wherein said electrolyte comprises the lithium salts of the group that is selected from following composition: LiClO ₄LiBF ₄LiPF ₆LiAlCl ₄LiSbF ₆LiSCN; LiCF ₃SO ₃LiCF ₃CO ₂Li (CF ₃SO ₂) ₂LiAsF ₆LiN (CF ₃SO ₂) ₂LiB ₁₀Cl ₁₀Lower aliphatic carboxylic acid lithium; LiCl; LiBr; LiI; Chlorine boron lithium; The tetraphenyl borate lithium; Imide li; And their mixture.

34. the described electrochemical cell of claim 32, wherein in the nascent state of described electrochemical cell, described A is a sodium.

35. the described electrochemical cell of claim 30, wherein said second electrode comprises the insertion active material, and it is selected from the group of being made up of transition metal oxide, metal chalcogenide, carbon and their mixture.

36. the described electrochemical cell of claim 35, wherein said insertion active material is a graphite.

37. the described electrochemical cell of claim 6, wherein in the nascent state of described electrochemical cell, described electrode active material is represented by following general formula:

A _a(M′O) _cXO ₄Z _f，

Wherein 0＜c≤1, and X is selected from the group of following composition: P, As, Sb, Si, Ge, V, S and composition thereof, and wherein selects A, M ', X, a, c and f, to keep the electric neutrality of nascent state electrode active material.

38. the described electrochemical cell of claim 37, wherein in the nascent state of described electrochemical cell, described A is selected from the group that is made of periodic table I family and II family element and composition thereof.

39. the described electrochemical cell of claim 37, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is a lithium.

40. the described electrochemical cell of claim 39, wherein said electrolyte comprises the lithium salts of the group that is selected from following composition: LiClO ₄LiBF ₄LiPF ₆LiAlCl ₄LiSbF ₆LiSCN; LiCF ₃SO ₃LiCF ₃CO ₂Li (CF ₃SO ₂) ₂LiAsF ₆LiN (CF ₃SO ₂) ₂LiB ₁₀Cl ₁₀Lower aliphatic carboxylic acid lithium; LiCl; LiBr; LiI; Chlorine boron lithium; The tetraphenyl borate lithium; Imide li; And their mixture.

41. the described electrochemical cell of claim 39, wherein in the nascent state of described electrochemical cell, described A is a sodium.

42. the described electrochemical cell of claim 37, wherein said second electrode comprises the insertion active material, and it is selected from the group of being made up of transition metal oxide, metal chalcogenide, carbon and their mixture.

43. the described electrochemical cell of claim 42, wherein said insertion active material is a graphite.

44. the described electrochemical cell of claim 37, (M ' O) is the 2+ valency ion that contains 4+ valency metal (M ') to wherein said component.

45. the described electrochemical cell of claim 37, wherein said M ' are vanadium (V), and XY ₄=PO ₄

46. the described electrochemical cell of claim 6, wherein in the nascent state of described electrochemical cell, described electrode active material is represented by following general formula:

A _aM _bWO ₄，

Wherein:

(i) component A and M as mentioned above, 0＜a≤2 and 0＜b≤1 wherein; And

(ii) W is selected from the group of following composition: Hf, Ti, Zr and composition thereof; And

Wherein, select A, M, W, a and b, to keep the electric neutrality of nascent state material.

47. the described electrochemical cell of claim 46, wherein in the nascent state of described electrochemical cell, described A is selected from the group that is made of periodic table I family and II family element and composition thereof.

48. the described electrochemical cell of claim 46, wherein in the nascent state of described electrochemical cell, described electrolyte charge carrier is a lithium.

49. the described electrochemical cell of claim 48, wherein said electrolyte comprises the lithium salts of the group that is selected from following composition: LiClO ₄LiBF ₄LiPF ₆LiAlCl ₄LiSbF ₆LiSCN; LiCF ₃SO ₃LiCF ₃CO ₂Li (CF ₃SO ₂) ₂LiAsF ₆LiN (CF ₃SO ₂) ₂LiB ₁₀C1 ₁₀Lower aliphatic carboxylic acid lithium; LiCl; LiBr; LiI; Chlorine boron lithium; The tetraphenyl borate lithium; Imide li; And their mixture.

50. the described electrochemical cell of claim 48, wherein in the nascent state of described electrochemical cell, described A is a sodium.

51. the described electrochemical cell of claim 46, wherein said second electrode comprises the insertion active material, and it is selected from the group of being made up of transition metal oxide, metal chalcogenide, carbon and their mixture.

52. the described electrochemical cell of claim 51, wherein said insertion active material is a graphite.

53. the described electrochemical cell of claim 46, wherein said M is selected from the group of following composition: Ni, Co, Fe, Mn, V, Cr and composition thereof.

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