CN105024049B - The material prepared by METAL EXTRACTION - Google Patents

The material prepared by METAL EXTRACTION Download PDF

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Publication number
CN105024049B
CN105024049B CN201510171088.8A CN201510171088A CN105024049B CN 105024049 B CN105024049 B CN 105024049B CN 201510171088 A CN201510171088 A CN 201510171088A CN 105024049 B CN105024049 B CN 105024049B
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lithium
metal
battery
active material
metal halide
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CN105024049A (en
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李斌
佟魏
杨仁贤
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Tianjin B&M Science and Technology Co Ltd
Wildcat Discovery Technologies Inc
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Tianjin B&M Science and Technology Co Ltd
Wildcat Discovery Technologies Inc
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Priority claimed from US14/253,764 external-priority patent/US9034516B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a kind of material prepared by METAL EXTRACTION.A kind of method that ion is extracted in active material from battery electrode is specifically disclosed, including the active material is mixed to form mixture with activating compounds.Mixture is annealed to extract a certain amount of ion from active material, a certain amount of oxygen is discharged from active material, and form activated active material.Embodiment of the present invention includes activated active material, the electrode and one-shot battery and secondary cell formed by this activated active material.

Description

The material prepared by METAL EXTRACTION
Technical field
The invention belongs to cell art, more specifically, belonging to the improved work for the electrode in electrochemical cell Property Material Field.
Background technology
Research to the active material of the negative electrode for secondary cell has generated a few class active materials.A kind of active material Material is the layered oxide (OLO) of " crossing lithiumation ", is expressed as：
xLi2MnO3·(1-x)Li[MniNijCok]O2
Wherein, 0≤x≤1, i+j+k=1, and i non-zero.This OLO materials are due to high specific capacity and as the next generation The promising candidate of battery.
However, OLO materials in an electrochemical cell first using being subjected to big irreversible capacity loss in circulation.With The battery that OLO materials make is assembled using the OLO materials of inactive form.In circulating first, by extracting Li simultaneously+Form Lithium and O2Or the oxygen of other oxygen-containing gas forms carrys out electrochemical activation non-activated materials.This activation method has multiple lack Point.First, gas is generated, it may produce problem in battery manufacture.Secondly, it may produce and lack in surface and main body Fall into, it may reduce high rate performance (rate capability), improve the speed of dissolving metal, and improve electrolyte oxidation Speed.3rd, the lithium of extraction may form unstable lithium material on anode, and it disturbs typical anode stability.
By being reacted with water-based acid such as hydrochloric acid (HCl) chemically to activate OLO.This activation method has multiple lack Point.First, this activation method needs excessive acid, and it may make it difficult to the degree for controlling lithium extraction so that extraction deficiency The lithium of amount or excess.Secondly, water and/or proton may be incorporated into any room caused by activation, and this may cause difference Cycle life and high rate performance (rate performance).3rd, because the chemistry in the waste water of this method is dirty Thing is contaminated, the cost for handling the waste water may be higher so that this method is difficult to scale.
Some have been carried out using organic fluoride such as polyvinylidene fluoride (PVdF) and polytetrafluoroethylene (PTFE) (PTFE) to come The research of basic ion is removed from metal oxide.In some researchs, both basic ion and oxygen are removed using organic compound. See, e.g. T.Ozawa et al. Inorg.Chem, 49, (2010) 3044 and T.Ozawa et al. Inorg.Chem, 51 (11), (2012).The reaction be used to remove all basic ions in material.
In addition, to using aluminum fluoride (AlF3) coating carried out some to improve the chemical property of lithium-rich oxide Research.See, e.g. Scrosati, B. et al. Adv.Mater.2012,24,1192-1196 and Zheng, J.M. et al. J.Electrochem.Soc.2008,155 (10), A775-A782.In addition, U.S. Patent Publication 2013/0216701 discloses The AlF formed by the precursor comprising aluminum nitrate solution and ammonium fluoride solution3Coating.There is no AlF3It is used directly in coating process. The evidence of any chemical reaction between OLO and metallic compound is not shown in open source literature, without structure cell in OLO structures yet Any evidence changed.Coating process must be carried out under nitrogen or other oxygen-free atmospheres.In addition, International Publication WO 2006/ 109930 disclose using the alkoxide of elemental precursors such as metal, sulfate, nitrate, acetate, chloride or phosphate to wrap Cover lithium metal oxide material.
To the LiNiO of rechargeable battery2De- lithium carried out some research.See, e.g. Arai, H. etc. Electrochem.Acta 2002,47,2697 (using sulfuric acid) and Arai, H. et al. J.Power Sources 1999, 81-82,401 (use NOPF6).Using NOPF6Research in, PF6With LiNiO2React and produce LiPF6Salt and NO gases. In the reaction, all F atoms keep being combined with phosphorus.In addition, although NOPF6Excessive (NOPF6/LiNiO2, but de- lithium journey=2) Degree is very low.
Still need by control lithium extraction come pre-activate OLO active materials it is effective, can scale means, for manufacturing For one-shot battery and the full battery of secondary cell.
The content of the invention
According to some embodiments of the present invention, there is shown herein for reducing the irreversible of lithium-rich oxide material The method of capacitance loss.
According to some embodiments of the present invention, the method for ion is extracted from the active material for battery electrode to be included The active material is mixed to form mixture with activating compounds.Mixture is annealed certain to be extracted from active material The ion of amount, a certain amount of oxygen is discharged from active material, and form the active material of activation.By reaction product optionally with warp The active material of activation separates, and forms battery electrode.Embodiment of the present invention includes activated active material, by this Electrode, one-shot battery and the secondary cell that the activated active material of kind is formed.
According to some embodiments of the present invention, the oxidate for lithium material such as lithium transition-metal oxygen for battery electrode is activated The method of compound material includes mixing oxidate for lithium material and a certain amount of activating compounds to form mixture.Will be described mixed Compound is annealed, to extract the lithium of controlled quatity by the way that the amount of activated material in mixture is pre-selected.On-gaseous can be formed Oxygen reaction product.
According to some embodiments of the present invention, the method for basic ion is extracted from material including by the material and necessarily The activating compounds of amount are mixed to form mixture, wherein the activating compounds are the organohalogen compounds of nonfluorinated.Will mixing Thing annealing is with the basic ion of the extraction controlled quatity from active material.The amount is by being pre-selected the amount of activated material in mixture To control.On-gaseous oxygen reaction product can be formed.
Brief description of the drawings
Fig. 1 shows the voltage curve of conventional OLO materials, and depicts the irreversible capacity loss after circulation first.
Fig. 2 shows voltage curve of the conventional OLO materials compared with material according to embodiments of the present invention, and retouches The improvement of irreversible capacity loss after circulating first is painted.
Fig. 3 shows voltage curve of the conventional OLO materials compared with material according to embodiments of the present invention, and retouches The improvement of irreversible capacity loss after being circulated first in the full battery with carbon anode is painted.
Fig. 4 data are indicated in the full battery with carbon anode compared with conventional material according to the chemical combination of the present invention Performance improvement caused by thing and method.
Fig. 5 shows voltage curve of the conventional OLO materials compared with material according to embodiments of the present invention, and retouches The improvement of irreversible capacity loss after circulating first is painted.
Fig. 6 shows figure of the conventional OLO materials compared with material according to embodiments of the present invention, and depicts again The improvement of rate performance.
Fig. 7 A, 7B and 7C are respectively scanning electron micrograph, depict conventional material (Fig. 7 A), grinding-material (Fig. 7 B) With the form of material (Fig. 7 C) mixed using low energy method.Low energy method maintains original form substantially.
Fig. 8 shows voltage curve of the conventional OLO materials compared with material according to embodiments of the present invention, and retouches The improvement of irreversible capacity loss after circulating first is painted.
Fig. 9 is shown in which that cathode material carries out the voltage curve of the one-shot battery of de- lithium according to an embodiment of the present invention.
Figure 10 A, 10B, 10C and 10D show conventional rich lithium NMC materials and richness preactivated according to an embodiment of the present invention The X-ray diffractogram of lithium NMC materials.
Figure 11 shows conventional rich lithium NMC materials compared with rich lithium NMC materials preactivated according to an embodiment of the present invention Compared with voltage curve, and depict first circulation after irreversible capacity loss improvement.
Figure 12 graphically depict conventional rich lithium NMC materials and rich lithium NMC materials preactivated according to an embodiment of the present invention Circulation coulombic efficiency first.
Figure 13 depicts conventional rich lithium NMC materials and rich lithium NMC materials preactivated according to an embodiment of the present invention with figure Cyclic discharge capacity first.
Figure 14 depicts conventional rich lithium NMC materials and rich lithium NMC materials preactivated according to an embodiment of the present invention with figure Circulating ratio performance.
Embodiment
The some aspects of the invention defined below for being applied to some embodiments description on the present invention.These definition Equally it can extend accordingly.Each term is explained further and illustrated by specification, drawings and examples.Term in present specification Any explanation be considered as set forth herein entire specification, drawings and examples.
The noun that unused numeral-classifier compound limits includes plural number, unless the context clearly dictates otherwise.Thus, for example, mentioning pair As when, it may include multiple objects, unless the context clearly dictates otherwise.
Term " substantially " and " basic " refer to sizable degree or scope.In use, should when binding events or situation Term can refer to the example that wherein event or situation accurately occur and the wherein example of the very approximate generation of the event or situation, Such as explain the changeability of common tolerance levels or embodiment described herein.
Term " about " refers to the scope of the value of very close set-point, with explain common tolerance levels, measurement accuracy or Other changeabilities of embodiment described herein.
Term " transition metal " refers to the chemical element of the race of the periodic table of elements the 3rd to 12, including scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver-colored (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), golden (Au), mercury (Hg), Lu Jin (Rf), Jin Du (Db), Jin happinesses (Sg), Jin ripples (Bh), Jin black (Hs) With Jin wheats (Mt).
Term " halogen " refers to any chemical element of the race of the periodic table of elements the 17th, including fluorine (F), chlorine (Cl), bromine (Br), Iodine (I) and astatine (At).
Term " oxygen group elements " refers to any chemical element of the race of the periodic table of elements the 16th, including oxygen (O), sulphur (S), selenium (Se), tellurium (Te) and polonium (Po).
Term " alkali metal " refers to any chemical element of the race of the periodic table of elements the 1st, including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) and francium (Fr).
Term " alkaline-earth metal " refers to any chemical element of the race of the periodic table of elements the 2nd, including beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra).
Term " rare earth element " refers to scandium (Sc), iridium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
Term " poor metal " refers to element aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), lead (Pb), bismuth (Bi) With polonium (Po).
Term " semimetal " refer to property between metal and it is nonmetallic between or with metal and nonmetallic mixture The chemical element of property, including boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), carbon (C), aluminium (Al), selenium (Se), polonium (Po) and astatine (At).
Term " metal " includes semimetal, poor metal, alkaline-earth metal, alkali metal and transition metal, each freedom of these terms Define herein.
Term " organic moiety " refers to carbon compound, and now term " organic " broadly understood in chemical field.
Term " specific capacity " refers to that the material of per unit mass can accommodate the electronics of (or release) or the amount (example of lithium ion Such as, total amount or maximum), and can be represented in units of mAh/g.In some aspects with embodiment, can be in constant current Measure specific capacity in electric discharge (or charging) analysis, it include relative to limited to electrode under stop voltage scope with restriction Multiplying power discharging (or charging).For example, can relative to Li/Li+ to electrode under 4.8V to 2.0V with about 0.05C (for example, about Discharged under multiplying power 12.5mA/g) to measure specific capacity.Other discharge-rates and other voltage ranges can also be used, e.g., from about 0.1C (for example, about 25mA/g) or about 0.5C (for example, about 125mA/g) or about 1.0C (for example, about 250mA/g) multiplying power.
Multiplying power " C " refers to (based on context) make battery (substantially completely charged state) substantially completely discharge in 1 hour As the fraction or the discharge current of multiple relative to " IC " current value, or make battery (substantially completely discharge condition) 1 Hour in substantially completely charge as the fraction or the charging current of multiple relative to " 1C " current value.
Term " NMC " refers to the formula (I) that nickel, manganese and cobalt wherein be present or the material of (II).Formula (II) describes rich lithium material Material, referred to herein as " OLO " material.
The degree that may change for some battery characteristics with temperature, these features are defined as at room temperature (about 30.DEG C), remove Non- context clearly states in addition.
Scope given herein includes its end points.Thus, for example, scope 1 to 3 include value 1 and 3 and between value.
Term " grinding " and " mixing " are used interchangeably, unless specifying the example of low energy mixed processing.In such case Under, material is mainly mixed rather than ground.
The composition of OLO active materials is represented by：
Li1+a[MnbNicCod]O2 (I)
Wherein 0.9≤a+b+c+d≤1.1, and b non-zeros.In its activated form, the material that formula (I) represents has lithium Ionic vacancies, therefore be represented by：
Li1+a-y[MnbNicCod]O2-x (II)
Wherein 0.9≤a+b+c+d≤1.1, and b non-zeros, 0.1≤y≤1.1, and 0≤x ＜ 2.Lithium ion loses Room is generated, is the transfer that this room promotes lithium ion in electrochemical cell in the active material that formula (II) represents.
According to certain embodiments of the present invention, the active material that formula (II) represents advantageously can be in assembling electrochemical battery Formed before, to avoid the significant irreversible capacity loss in the circulation first using electrochemical cell.In this embodiment party In case, the active material of formula (II) expression is formed by reaction summarized below：
Li1+a[MnbNicCod]O2+AB→LiB+AO2-x+Li1+a-y[MnbNicCod]O2-x (III)
Formula (I) formula (II)
Wherein A is organic moiety or metal；B is halogen or oxygen group elements；0≤x ＜ 2；A, b, c, d and y keep it in formula (I) value and in (II) limited.When according to embodiment of the present invention in use, " AB types " material of formula (III) can be described as living Change compound.Both the extractable alkali metal (such as lithium) of reaction and anion (such as oxonium ion).
In embodiments of the invention, oxidate for lithium material is reacted with AB compounds to cause lithium and halogen or chalcogen member Element reaction.In some embodiments, bifurcated alkali halide salts or bifurcated alkali chalcogenide salt are formd, and A large amount of chemical lithium deintercalations that are formed as of these salt provide thermodynamic driving force.
More generally, embodiment of the present invention be related to by with organohalogen compounds or organic chalcogenide pyroreaction from Metal is extracted in ceramic material.In this reaction, halogen or chalcogenide component are reacted with ceramics to form metal halide Thing or metal chalcogenides or complex compound.By this way, organohalogen compounds or organic chalcogenide extract from ceramics Metal.Preferably, metal is alkali metal or alkaline-earth metal.
One advantage of formula (III) reaction be easily before manufacture negative electrode from system it is any except discharging in dereaction Oxygen.Another advantage of formula (III) reaction is that the lithium of stoichiometric proportion is can extract in the material represented from formula (I).By advance Select control of the amount realization of activating compounds to reaction.By contrast, from formula (I) represent material in extract lithium it is some Perception method extracts lithium dependent on the circulation first of assembled battery.The lithium extracting method of this prior art may discharge oxygen, this Problem is produced in assembled battery, and does not allow stoichiometrically to control lithium to extract.
Another advantage of some embodiments is by the active material of pre-activate negative electrode, negative electrode effectively chemistry charging Rather than electrochemical charge., can be by these high-energy using the material of chemistry charging or activation, such as the material that formula (II) represents Density OLO materials or similar material manufacture one-shot battery.By contrast, conventional OLO materials are currently only used for secondary cell, at this In kind of battery, its can in charge/discharge cycle electrochemical activation.Therefore, the compounds of this invention can be used for active cell material Material, including remove alkali metal or alkaline-earth metal ions completely from cathode material, to enable these cathode materials to be used in one In primary cell.
For example, in the case where carrying out activated li nickel oxide cathode material using PVdF, at least two differential responses are can Can：
LiNiO2+C2H2F2→NiO2+LiF (IV)
Or
LiNiO2+C2H2F2→NiO2-x+ LiF+xCO (or CO2) (V)
Formula (V) shows a case that oxygen is released and reacted with PVdF carbon.Other reaction products can be formed, including but not It is limited to CO, CO2、H2O、CO2F, C and/or CxHy。
According to embodiment of the present invention, the reaction pre-activate OLO materials represented by formula (III), OLO materials are reduced In irreversible capacity loss.Organohalogen compounds, organic chalcogenide and metal halide contribute to the change of OLO materials Learn the preferred material of activation.According to some embodiments, activation method, which uses, to be used to form the moon based on lithium-rich oxide The conventional material of pole material, such as Li2CO3、LiOH、Ni(OH)2、NiO、NiOOH、NiCO3、MnO2、Mn2O3、MnCO3、CoO、 Co2O3With Co (OH)2, and Li, Ni, Mn and Co various nitrate, sulfate, halide and acetate.Use conventional grinding Method or mixed method grind these raw material together with the activating compounds that formula (III) represents, the activating compounds example Such as organohalogen compounds, organic chalcogenide, metal halide or its combination.Then the ground mixture is annealed.
A is metal preferred as alkali or alkaline-earth metal in the embodiment of formula (III) of metal wherein.A is wherein In some embodiments of the formula (III) of metal, metal can be transition metal.A is some of the formula (III) of metal wherein In embodiment, metal can be the periodic table of elements the 13rd, 14 or the element or rare earth element of 15 races.
A is that organic moiety preferably comprises and alkali metal or alkaline earth in the embodiment of formula (III) of organic moiety wherein Metal forms the functional group of stable comple.The example of the organic moiety of preferred type include fluoropolymer, chlorine-containing polymer, Carbon halogenide, alkyl fluoride, aryl fluorides and combinations thereof.The example of preferable fluoropolymer includes PVdF and PTFE. The example of preferable chlorine-containing polymer includes polyvinyl chloride (PVC).The example of preferable carbon halogenide includes single fluorocarbons (CFx).The example of preferable aryl fluorides includes eight naphthalene fluorides.
B is that the halogen is not fluorine in some embodiments of formula (III) of halogen wherein.In such embodiment party In case, the AB materials of preferably formula (III) are the organohalogen compounds based on chlorine, such as polyvinyl chloride (PVC).PVC is relatively low The organohalogen compounds of cost, therefore the effective scale that activation method will be allowed.
B is in some embodiments of formula (III) of oxygen group elements wherein, the preferred cadmium telluride of AB compounds, indium sulfide, Zinc telluridse or sodium selenide.
Do not limited by any particular theory or the mode of action, annealing process can promote " B " material and included in negative electrode original The reaction of lithium in material.For example, high temperature can promote the reaction of fluorine and the lithium included in layered oxide material.In addition, " A " Material can react with any oxygen discharged during this.For example, organic " A " material (such as carbon) can react shape with the oxygen of release Into CON.This process has obtained the OLO materials of a certain amount of lithium for discharging or extracting in advance, and provides and circulated first In improvement to observed irreversible capacity loss.
According to some embodiments, grinding by conventional grinding methods completion, such as ball milling or other substantially equivalent grind Mill method.
In certain embodiments, the material of particle shape is kept for wherein low energy mixed method, preferably low energy mixes Method.Grinding can make particle deformation, and some ceramics or cathode material that therefrom extract metal benefit from low energy mixed method.
According to some embodiments, the mixture annealing time enough that will be ground or mix at relatively high temperature. Suitable temperature range can be about 150 DEG C to about 800 DEG C, about 200 DEG C to about 800 DEG C, about 250 DEG C to about 800 DEG C, about 300 DEG C to about 800 DEG C, about 350 DEG C to about 800 DEG C, about 400 DEG C to about 800 DEG C, about 450 DEG C to about 800 DEG C, about 500 DEG C to about 800 DEG C, about 550 DEG C to about 800 DEG C, about 600 DEG C to about 800 DEG C, about 650 DEG C to about 800 DEG C, or about 700 DEG C to about 800 DEG C.It is preferred that Temperature range can be about 200 DEG C to about 600 DEG C.
Annealing time can be about 0 hour to about 24 hours.It is highly preferred that annealing time be about 1 hour to about 6 hours, About 1.5 hours to about 6 hours, about 2.0 hours to about 6 hours, about 2.5 hours to about 6 hours, about 3.0 hours to about 6 hours, About 3.5 hours to about 6 hours, about 4.0 hours to about 6 hours, about 4.5 hours to about 6 hours, or it is about 5.0 hours to about 6 small When.
While characterized as embodiment of the present invention be but some embodiment party on extracting lithium from OLO materials Case is related more generally to by being activated with organohalogen compounds, organic chalcogenide, metal halide or disclosed herein other Material at high temperature is reacted to extract alkali metal from ceramic material.Certain embodiments as disclosed herein can be activated beyond OLO materials Battery material, and available for extracting basic ion, such as lithium from the active material of one-shot battery.
In certain embodiments, using metal halide pre-activate, (or any electrochemistry in assembled battery is lived Chemical activation before change) lithium-rich oxide.For example, can by directly with metal fluoride reaction come pre-activate lithium-rich Oxide, the metal fluoride such as AlF3、MgF2、BF3、CaF2、CoF2、TiF3、MnF2、NiF2And combinations thereof.
By coprecipitation disclosed herein prepare the cathode material based on lithium-rich oxide, then with metal halide Thing such as BF3Or TiF3Annealing is with material described in pre-activate.This method obtains extracting the stratiform of a certain amount of lithium before full battery is assembled Oxide material, and provide to important battery performance feature as observe irreversible capacity loss in terms of significantly change It is kind.
Do not limited by any particular theory or the mode of action, in some reactions disclosed herein, fluoride components with Lithium-rich oxide is reacted to form the composition that following formula represents：
MxM′yXz (VI)
Wherein M and M ' is respectively metal, and X is oxygen or fluorine or combination.For example, in OLO materials Li [Li0.2Mn0.54Ni0.13CO0.13]O2In, M=Li；M '=Li, Mn, Ni, Co；X=0.Metal M is preferably alkali metal or alkaline earth gold Category, M ' is transition metal, poor metal, semimetal, alkali metal or alkaline-earth metal.
In addition, in some reactions, fluorine is reacted with lithium-rich oxide material main body to form fluorination lithium-rich oxygen Compound.That is, some oxygen sites are doped with fluorine (or other halogens, when using other halogens as precursor).Before metal halide The metal of body can be reacted with the oxygen from some reactions to form the compound that following formula represents：
M′Oy. (VII)
Wherein M ' can be alkali metal, alkaline-earth metal, transition metal, poor metal or semimetal.Further, metal halide Metal in thing precursor can also be doped in lithium-rich oxide.
Following examples set forth the particular aspects of some embodiments of the invention, to illustrate to those skilled in the art With offer description.Embodiment should not be construed as the limitation present invention, can be used for understanding and putting into practice this hair because embodiment provide only The ad hoc approach of some bright embodiments.
Embodiment
The lithium-rich oxide of secondary cell
Half-cell
Material and synthetic method.All reactions are in glove box (M-Braun, oxygen and the moisture of high-purity argon filling ＜ 0.1ppm) in prepare.Unless otherwise indicated, material is obtained from commercial source (Sigma-Aldrich, Advanced Research Chemicals Inc, Alfa Aesar, etc.) and be not required to be further purified.
Layered oxide activates：Organohalogen compounds and lithium-rich oxide material are mixed using Ginding process.One In a little examples, low energy mixed method is used.Organic halide precursors (5wt%), lithium-rich oxidation are loaded into grinding container Thing and optional solvent, such as acetone.Then container is sealed and ground.After grinding, evaporated at 60 DEG C in mixture Solvent, then mixture is annealed at e.g., from about 350 DEG C to about 450 DEG C in atmosphere.Flushing or other method can be passed through Optionally take out reaction product.
Electrode is prepared.Using 85: 7.5: 7.5 (active materials: adhesive: conductive additive) preparation compositions according to Lower compound method prepares the negative electrode of the layered oxide material based on activation：198mg PVdF (Sigma Aldrich) are existed Dissolved overnight in 15mL NMP (Sigma Aldrich).198mg conductive additives are added into solution and are stirred a few hours.So The layered oxide material of 150mg activation is added in this solution of backward 1mL and is stirred overnight.By the way that about 50 μ L slurries are dripped Fall on stainless steel current-collector and dried about 1 hour at 150 DEG C and carry out cast membrane.Cool down dry film, then in 1 ton/cm2Under Pressurization.By electrode under vacuo in 150 DEG C of re-dries 12 hours, enter afterwards in glove box and be used for battery and assemble.
Electrochemical Characterization.Unless otherwise stated, in glove box (M-Braun, the O of high-purity argon filling2Contain with moisture Measure ＜ 0.1ppm) in all batteries of assembling.Using as in the lithium of anode, Celgard2400 dividing plates and 90 μ L 1: 2EC: EMC 1M LiPF6 electrolyte fabrication half-cells.Under 4.7V to 2.5V constant current C/10 charging and discharging multiplying power, 25 DEG C electrochemical Characterization is carried out to electrode and battery.Do not include constant voltage step.
The lithium-rich oxide of secondary cell (full battery)
Material and synthetic method.All reactions are in glove box (M-Braun, oxygen and the moisture of high-purity argon filling ＜ 0.1ppm) in prepare.Unless otherwise indicated, material is obtained from commercial source (Sigma-Aldrich, Advanced Research Chemicals Inc, Alfa Aesar, etc.) and be not required to be further purified.
Layered oxide activates：Organohalogen compounds and OLO materials are mixed using Ginding process.Loaded into grinding container Organohalogen compounds precursor (5wt%), OLO and optional solvent, such as acetone.Then container is sealed and ground.After grinding, The solvent in mixture is evaporated at 60 DEG C, then mixture is annealed at 450 DEG C in atmosphere.Can by rinse or its The optional taking-up reaction product of his method.
Electrode is prepared.Using 85: 7.5: 7.5 (active materials: adhesive: conductive additive) preparation compositions according to Lower compound method prepares the negative electrode of the layered oxide based on activation：By 198mg PVdF (Sigma Aldrich) in 15mL Dissolved overnight in NMP (Sigma Aldrich).198mg conductive additives are added into solution and are stirred a few hours.Then to The layered oxide material of 150mg activation is added in this solution of 1mL and is stirred overnight.By the way that about 66 μ L slurries are dropped onto On stainless steel current-collector and dried about 1 hour at 150 DEG C and carry out cast membrane.Cool down dry film, then in 1 ton/cm2It is lower to add Pressure.By electrode under vacuo in 150 DEG C of re-dries 12 hours, enter afterwards in glove box and be used for battery and assemble.
Using 85: 7: 8 (active materials: adhesive: conductive additive) preparation compositions according to following compound method come Prepare the anode based on MCMB (mesopore carbosphere)：By 132mg PVdF (Sigma Aldrich), 115mg conductive additives and 1400mg MCMB dissolve overnight in 10mL NMP (Sigma Aldrich).By the way that about 50 μ L slurries are dropped onto into stainless steel collection On electrical equipment and dried about 1 hour at 150 DEG C and carry out cast membrane.Cool down dry film, then in 1 ton/cm2Lower pressurization.By electrode Under vacuo in 150 DEG C of re-dries 12 hours, enter afterwards in glove box and be used for battery and assemble.
Electrochemical Characterization.Unless otherwise stated, in glove box (M-Braun, the O of high-purity argon filling2Contain with moisture Measure ＜ 0.1ppm) in all batteries of assembling.Using the MCMB as anode, the dividing plates of Celgard 2400 and 90 μ L 1: 1EC: EMC In the full battery of 1M LiPF6 electrolyte fabrications.Under 4.6V to 2.0V constant current C/20 charging and discharging multiplying power, 30 DEG C carry out electrochemical Characterization to electrode and battery.
The lithium nickel oxide of the de- lithium of one-shot battery
Material and synthetic method.All reactions are in glove box (M-Braun, the O of high-purity argon filling2And moisture ＜ 0.1ppm) in prepare.Unless otherwise indicated, material is obtained from commercial source (Duracell) and is not required to be further purified.
Lithium nickel oxide takes off lithium.Organohalogen compounds and lithium nickel oxide are mixed using low energy mixed method.Hold to mixing Organic halide precursors (70 mol ratio) and lithium nickel oxide are loaded in device.Then by mixture under an inert atmosphere in about 450 DEG C annealing about 6 hours.
Electrode is prepared.It is based on using the preparation compositions of 79: 21 (de- lithium materials: carbon) according to following compound method to prepare The negative electrode of lithium nickel oxide：1g is taken off into lithium material and 267mg carbon mixes, then adds 66.7 μ L KOH (9M).450mg is abundant The material of mixing is transferred in cathode can and manual pressure.2.4g Zn slurries are added in anode can and pass through insulator ring Closing.Dividing plate is soaked with KOH (9M) and is placed in cellophane tape towards cathodic coating in cathode can.With hand by cathode can and anode Tank is nested together.
Electrochemical Characterization.Assembled battery in atmosphere.About 2.5v to about 0.2v constant current C/40 charging and put Under electric multiplying power, electrochemical Characterization is carried out to electrode and battery at 25 DEG C.Do not include constant voltage step.
The lithium-rich oxide activated with metal fluoride
Material and synthetic method.All reactions are carried out in atmosphere.Unless otherwise indicated, material is obtained from commercial source (example Such as, Sigma-Aldrich or Fisher Scientific) and need not be further purified.
The synthesis of lithium-rich oxide material.Lithium-rich oxide material is prepared by coprecipitation.Use metal Precursor of the nitrate as Li, Mn, Ni and Co component of lithium-rich oxide material.The precursor that former state receives is dissolved in In ionized water.Gained metal nitrate salt mixture is mixed according to the stoichiometric proportion of objective composition.To mixing NH is slowly added in metal-nitrate solutions4HCO3As coprecipitator.It is after mixing 0.5 hour, solution is dried at 60 DEG C Night.Then dry material is heated to 200 DEG C and kept for 3 hours.Then, material is annealed 10 hours at 900 DEG C.It is all dry Dry, heating and annealing steps are carried out in atmosphere.
By directly reacting activation layered oxide with metal fluoride.Using commercial metals fluoride (for example, coming from Sigma-Aldrich BF3.2H2O or TiF3) it is used as precursor.5mL deionized waters are added to and synthesize step more than containing 500mg In the rapid crucible of the rich lithium material of synthesis as former state.The BF of selected amount is added into crucible3.2H2O.Gained crucible contents are mixed 0.5 hour, then it is dried overnight at 60 DEG C.Dry material is annealed 6 hours at 400 DEG C.Annealing steps can be in air or nitrogen Carried out in gas.
With metal nitrate and ammonium fluoride activation layered oxide.In some cases, using commercial metals nitrate and NH4F solution is respectively as the metal of reaction and the source of fluorine.Metal fluoride precursor, the Fu Li of specified amount are loaded into crucible Layered oxide and deionized water simultaneously mix 0.5 hour.Solution is dried, then annealed in atmosphere.These materials provide Comparative example for the experiment for embodiment of the present invention.
Electrode is prepared.Active material using 80: 10: 10: adhesive: the preparation compositions of conductive additive are prepared and are based on The negative electrode of the layered oxide of activation.Specifically, by 198mg adhesives (polyvinylidene fluoride from Sigma-Aldrich) Dissolving is stayed overnight in 11mL solvents (METHYLPYRROLIDONE from Sigma-Aldrich).198mg is added into solution Conductive additive simultaneously stirs a few hours.Then the layered oxide material of 144mg activation is added into this solution of 1mL (with production Raw desired 80: 10: 10 ratio) and be stirred overnight.By the way that about 50 this slurries of μ L are dropped onto on stainless steel current-collector so Dried about 1 hour at 150 DEG C afterwards and carry out cast membrane.Cool down dry film, then in 1 ton/cm2Lower pressurization.Then will be pressurized Electrode film is under vacuo in 150 DEG C of re-dries 12 hours.
Electrochemical Characterization.Unless otherwise stated, in glove box (M-Braun, the O of high-purity argon filling2Contain with moisture Measure ＜ 0.1ppm) in all batteries of assembling.Using the lithium as anode, Celgard2400 dividing plates and ethylene carbonate (EC)： 90 μ L 1M LiPF in the organic solvent of 1: 2 mixture of ethyl methyl carbonate (EMC)6Electrolyte direct-assembling electricity Pond.Under 4.8V to 2.0V constant current C/10 (25mA/g) charging and discharging multiplying power, electrode and battery are entered at 30 DEG C Row electrochemical Characterization.Do not include constant voltage step.
As a result
Fig. 1 be show conventional OLO materials circulate first after irreversible capacity loss voltage curve.What is measured is this The conventional coulombic efficiency (mark is CE " in figure) for not improving material is 78%.In initial charge-discharge cycles, there is 71mAh/ G irreversible capacity losses.Fig. 1 shows the irreversible capacity loss of prior art OLO materials.
Fig. 2 is shown compared with conventional material using the irreversible of Compounds and methods for according to embodiments of the present invention The improved voltage curve of capacitance loss.Use PVdF as " AB " material (organic fluoride) to OLO materials in the above-mentioned methods Expect chemical lithium deintercalation.Fig. 2 shows the improvement of irreversible capacity loss --- chemical lithium deintercalation material (labeled as " PVdF processing ") 24mAh/g in contrast to conventional material 71mAh/g.The coulombic efficiency of the chemical lithium deintercalation material of measurement is 91%.
Fig. 3 is shown compared with conventional material using the irreversible of Compounds and methods for according to embodiments of the present invention The improved voltage curve of capacitance loss.Chemical lithium deintercalation material shows improved irreversible capacity loss.Using carbon anode Full battery in measure material.The 76mAh/g of irreversible capacity loss from conventional OLO materials has been improved to PVdF chemical lithium deintercalations OLO materials 49mAh/g.Coulombic efficiency has been improved to the OLO materials with PVdF chemical lithium deintercalations from the 77.2% of conventional OLO materials The 82.0% of material.
Fig. 4 is tables of data, is shown in the full battery with carbon anode compared with conventional material according to the change of the present invention Performance improvement caused by compound and method.Top row compares conventional OLO materials and OLO materials through PVdF chemical lithium deintercalations first The actual irreversible capacity loss of circulation.The irreversible capacity loss of OLO materials is about 80mAh/g to about 75mAh/g, and chemical The irreversible capacity loss of de- lithium material is about 55mAh/g.Center row compares conventional OLO materials and through PVdF chemical lithium deintercalation The percentage for the irreversible capacity loss that OLO materials circulate first.The irreversible capacity loss of OLO materials is about 31% to about 29%, and the irreversible capacity loss of chemical lithium deintercalation material is about 25% to about 24%.Bottom line compare conventional OLO materials and The coulombic efficiency of OLO materials through PVdF chemical lithium deintercalations.The coulombic efficiency of OLO materials is about 77%, and chemical lithium deintercalation material Coulombic efficiency is about 81%.
Fig. 5 is voltage curve of the conventional rich lithium material compared with the de- lithium material using PVdF chemistry.Fig. 5, which is shown, to be passed through Chemical lithium deintercalation is carried out to OLO materials, irreversible capacity loss is reduced to 3.9% from 18.7%, without reducing specific capacity.Separately Outside, Fig. 5 shows that the coulombic efficiency of initial charge has brought up to the 96.1% of chemical lithium deintercalation material from 81.3%.
Fig. 6 be by chemical lithium deintercalation conventional OLO materials (circle) and do not carry out chemical lithium deintercalation conventional OLO materials (side Shape) high rate performance compared.The OLO materials that (that is, chemical lithium deintercalation) is activated according to embodiment disclosed herein show improvement High rate performance.In some cases, chemical activation method makes the high rate performance of OLO materials mentioned from 64.5% 76.1%.
Fig. 7 A, 7B and 7C are respectively the scanning electron microscope diagram of multiple material according to embodiments of the present invention.Fig. 7 A It is the figure for the OLO materials that untreated former state receives.Fig. 7 B are the figures of the OLO materials handled using ball milling mixing method.Fig. 7 C It is the figure of the OLO materials handled using low energy mixed method, and Fig. 7 C show that low energy mixed method maintains initial configuration.Weight If, as seen in figure 7 c, the performance improvement shown in Fig. 5 and Fig. 6 is realized, and do not change primary granule form (figure 7A).Using low energy mixed method, maintain the form for receiving particle as former state, at the same still improve irreversible capacity loss and High rate performance.
Fig. 8 is the voltage that conventional OLO materials (solid line) compare with the identical material (dotted line) using PTFE chemical lithium deintercalations Curve.Fig. 8 shows that irreversible capacity loss is reduced to 5.5% from 18.7%, and similar specific capacity is maintained between material.
Table 1 provides the summary for the data that conventional OLO materials are compared with the identical material using PVdF chemical lithium deintercalations.Table 1 Show, chemical lithium deintercalation material has similar or more preferable capacity, coulombic efficiency, high rate performance and cycle life.
Table 1
Fig. 9 is with the LiNiO that lithium is taken off using PVdF2The voltage curve of the one-shot battery of cathode material.Fig. 9 displays use The extraction efficiency of PVdF solid lithium extracting method about 70%.From these results, it should be understood that, it is necessary to PVdF and nickel oxide former material The ratio of material is more than 100% with to LiNiO2Completely de- lithium.
Figure 10 A, 10B and 10C show the rich lithium NMC materials of control and and same amount metal fluoride (in the case, is not BF3) reaction the X-ray diffractogram compared of rich lithium NMC materials.Figure 10 A depict the gamut of diffraction pattern, and Figure 10 B and figure 10C respectively depict the peak that " B " and " C " are circled and be respectively labeled as in diffraction pattern.The BF of differential responses3Amount be 0.7 Weight %, 1.3 weight % or 2 weight %.It is main phase that Figure 10 A, which are shown in rich lithium NMC materials in all test samples,.But With BF3The increase of concentration, the main diffraction maximum around 37 ° of 28' and 44 ° of 28' have systematically been displaced to less than 28 °.Although scheming Do not depicted in 10A, 10B or 10C, but work as BF3When content increases to above 2 weight %, that does not observe these peaks enters one Step skew.As shown in Figure 10 D, when using AlF3During as activated precursors, this skew is not observed.
These peaks show the increasing of one or more lattice parameters of the crystalline phase of rich lithium NMC materials to less than 28 ° skews Greatly.Lattice dilation meets the mechanism that such as reactant has been doped in rich lithium NMC materials.For example, fluorine atom can be doped to rich lithium The oxygen position of NMC materials, it will increase at least one lattice parameter.
Figure 10 A, 10B and 10C data show that metal fluoride materials produce reaction product with the reaction of rich lithium NMC materials. Reaction product is structurally different from untreated rich lithium NMC.By contrast, when coating rich lithium NMC materials with metal fluoride, X-ray diffractogram is by the superposition of the diffraction pattern for showing original rich lithium NMC materials and the diffraction pattern of metal fluoride.That is, Fu Li There is no peak skew in NMC materials, but the other peak related to metal fluoride materials is will appear from diffraction pattern.
Figure 11 is shown compared with conventional material (the rich lithium NMC materials of synthesis as former state) using the chemical combination according to the present invention The improved a series of voltage curve of irreversible capacity loss when thing and method.Figure 11 is shown with BF3The increase of concentration can not The improvement of inverse capacity.By using various amounts (including 0.7 weight %, 1.3 weight % and 2 weight %) BF3Pre-activate is closed as former state Into rich lithium NMC, generate improved material.Irreversible capacity is reduced to from 15.1% in untreated rich lithium NMC materials Use 2wt%BF35.5% in the rich lithium NMC materials of pretreatment, and there is no any reduction than discharge capacity.In addition, Figure 11 is said Bright, the coulombic efficiency measured in initial charge has been increased to from 84.9% in untreated rich lithium NMC materials and has used 2wt%BF3 The 94.5% of the rich lithium NMC materials of pretreatment.
Table 2 is provided with (being in the case BF with metal halide3) preactivated material is compared to conventional rich lithium NMC materials The summary of the data of material.Table 2 shows irreversible capacity loss and the storehouse of the electrode formed by using metal halide pre-activate The improvement of human relations efficiency.Especially, when irreversible capacity and coulombic efficiency improve, discharge capacity keeps substantially constant.In order to produce Data in raw table 2, make battery at 30 DEG C between 4.8v and 2.0v with C/10 circulation.
Table 2
Electrode during Figure 12 is shown between 30 DEG C of temperature and 4.8V and 2.0V with the battery of 0.1C circulation The circulation coulombic efficiency first of material.Left column shows the data of control material (the rich lithium NMC materials of synthesis as former state) (with fact Heart circle represents).Open circles are represented by by directly reacting preactivated according to the metal fluoride of the embodiments described herein The data that electrode material is collected.Specifically, open circles are equivalent to using AlF3(the weight % of concentration 4.4 and 6.2 weight %), BF3 (the weight % of concentration 0.7,1.3 weight % and 2 weight %) and TiF3(the weight % of concentration 1,2 weight % and 3 weight %) pre-activate Former state synthesis rich lithium NMC.Each pre-activate material, AlF3、BF3And TiF3Display is dropped with concentration dependent coulombic efficiency It is low.Figure 12 shows the data from further embodiment, wherein using some metal nitrates and NH4F solution is as precursor.
Electrode during Figure 13 is shown between 30 DEG C of temperature and 4.8V and 2.0V with the battery of 0.1C circulation The cyclic discharge capacity first of material.Left column shows the data of control material (the rich lithium NMC materials of synthesis as former state) (with fact Heart circle represents).Open circles are represented by directly reacting preactivated electricity according to the metal fluoride of the embodiments described herein The data that pole material is collected.Specifically, open circles are equivalent to using AlF3(the weight % of concentration 4.4 and 6.2 weight %), BF3It is (dense Spend 0.7 weight %, 1.3 weight % and 2 weight %) and TiF3(the weight % of concentration 1,2 weight % and 3 weight %) preactivated original The rich lithium NMC of sample synthesis.Figure 13 shows comparable discharge capacity in multiple pre-activate examples.As Figure 12, triangle Expression uses metal nitrate and NH4F solution is as precursor.
Figure 14 shows the forthright again of electrode material in the battery circulated between 30 DEG C of temperature and 4.8V and 3.0V Energy (percentage for being maintained at the 0.1C high rate performances under 1C discharge-rates).Left column shows that control material (synthesizes as former state Rich lithium NMC materials) data (being represented with filled circles).Open circles represent to pass through the metal fluorine according to the embodiments described herein Compound directly reacts the data that preactivated electrode material is collected.Specifically, open circles are equivalent to using AlF3(the weight of concentration 4.4 Measure % and 6.2 weight %), BF3(the weight % of concentration 0.7,1.3 weight % and 2 weight %) and TiF3(the weight % of concentration 1,2 weights Measure % and 3 weight %) the rich lithium NMC of preactivated former state synthesis.Figure 14 shows further embodiment, and its display uses metal The high rate performance of the rich lithium NMC materials of the chemical activation step of fluoride.AlF3And NH4F shows as 1C capacity and remained above 85%.
The improvement of coulombic efficiency is applicable to other ceramic materials (for example, super cathode materials for lithium battery).
Further, the metal halide based on chlorine can act on similar to the mode of metal fluoride, but be used as more Low cost selection is (for example, AlCl3), as described in herein in regard to organohalogen compounds.In addition to lithium, metal chloride can be used for from Other basic ions or alkaline earth ion are extracted in layered oxide material.
Metal halide reaction disclosed herein can be used for activation one-shot battery material, have similar to use disclosed herein Machine halide activates one-shot battery.For example, by reacted with metal halide remove alkali metal ion or alkaline-earth metal ions can Cathode material is used in one-shot battery.
One important advantage of metal halide reaction disclosed herein is that reaction can be carried out in atmosphere.It is this anti- Answer feature provide compared to art methods efficiency and can scale significantly improve.
According to embodiment disclosed herein, chemical lithium deintercalation method can be used to improve conventional OLO materials, such as high rate performance Improve, and irreversible capacity loss is less than 5% in circulation first.These and other performance benefits are achieved without reducing other Performance, such as specific capacity.Particle shape can also be kept.
Although describing the present invention with reference to this paper particular, it will be appreciated that those skilled in the art that It can be variously changed and a variety of equivalent replacements can be carried out, without departing from the model of the invention being defined by the following claims Enclose.In addition, many change so that particular condition, material, the component of material, method or technique are suitable to mesh of the invention can be carried out , spirit and scope.All such modifications are included in scope of the following claims.Especially, it is although disclosed herein Method describes with reference to the specific operation performed with particular order, it should be appreciated that these operations are combined, subdivided or rearrange To form equivalent processes, without departing from the teachings of the present invention.Therefore, unless otherwise indicated herein, the order that otherwise operates and point Group does not limit the present invention.

Claims (20)

1. a kind of method for the active material for forming battery electrode, it includes：
The raw material for including lithium-rich oxide are provided, wherein the lithium-rich oxide is expressed as Lii+a[MnbNicCod] O2 (I)
Wherein 0.9≤a+b+c+d≤1.1, b non-zero；
The raw material are mixed with the activated material comprising metal halide compound；
Mixture is annealed a period of time in atmosphere at a certain temperature so that the raw material and the metal halide materialization Compound reaction is to form activated material, wherein the activated material is characterised by the lattice expanded compared with the raw material.
2. according to the method for claim 1, wherein the metal component of the metal halide be transition metal, poor metal, Semimetal, alkali metal or alkaline-earth metal.
3. according to the method for claim 1, wherein the metal component of the metal halide be selected from aluminium, boron, calcium, cobalt, manganese, Nickel, titanium and combinations thereof.
4. according to the method for claim 1, wherein the metal component of the metal halide is boron.
5. according to the method for claim 1, wherein the metal component of the metal halide is titanium.
6. according to the method for claim 1, wherein the activated material is selected from AlF3、BF3And TiF3。
7. according to the method for claim 1, wherein the raw material include lithium, manganese, nickel, cobalt and oxygen.
8. according to the method for claim 1, wherein the raw material include lithium, nickel and oxygen.
9. a kind of method for manufacturing battery, it includes：
Electrolyte is provided；
Anode is provided；
There is provided and include the negative electrode of the active material through chemical lithium deintercalation, wherein by make rich lithium raw material and metal halide reaction come Chemical lithium deintercalation is carried out to the active material, wherein the rich lithium materials statement is shown as
Lii+a[MnbNicCod]O2 (I)
Wherein 0.9≤a+b+c+d≤1.1, b non-zero,
Wherein described reaction includes making the rich lithium raw material anneal in atmosphere with the metal halide；
The wherein described active material through chemical lithium deintercalation is characterised by the lattice expanded compared with the rich lithium raw material；And
By the electrolyte, anode and cathode assembling into battery.
10. according to the method for claim 9, wherein the active material includes lithium, at least one transition metal and oxygen.
11. according to the method for claim 9, wherein the active material includes lithium, manganese, nickel, cobalt and oxygen.
12. according to the method for claim 9, wherein the active material includes lithium, nickel and oxygen.
13. according to the method for claim 9, wherein the battery is one-shot battery.
14. according to the method for claim 9, wherein the battery is secondary cell.
15. according to the method for claim 9, wherein the metal component of the metal halide be selected from aluminium, boron, calcium, cobalt, Manganese, nickel, titanium and combinations thereof.
16. according to the method for claim 9, wherein the metal component of the metal halide is boron, titanium or its combination.
17. according to the method for claim 9, wherein metal halide is selected from AlF3、BF3And TiF3。
18. a kind of battery, it includes the electrode formed as the method described in claim 9.
19. battery according to claim 18, wherein the battery is one-shot battery.
20. battery according to claim 18, wherein the battery is secondary cell.
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