CN101558518B - Cathode active material for nonaqueous electrolyte secondary battery and method of producing cathode active material for nonaqueous electrolyte secondary battery - Google Patents
Cathode active material for nonaqueous electrolyte secondary battery and method of producing cathode active material for nonaqueous electrolyte secondary battery Download PDFInfo
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Abstract
To prepare a fluorinated cathode active material having a guest cation comprising sodium or lithium included therein in a nonaqueous electrolyte secondary battery, an alkali metal fluoride represented by the formula AF and a transition metal fluoride represented by the formula M'F2 are treated by chemical milling to thereby give a fluoride AM'F3. A satellite ball mill is preferably employed in the chemical milling treatment.
Description
Technical field
The application requires the priority based on Japanese patent application 2006-311126 and Japanese patent application 2007-083634, and the disclosed content of this patent application is all quoted at this by reference.
The present invention relates to the rechargeable nonaqueous electrolytic battery that can discharge and recharge, the positive electrode active material for nonaqueous electrolyte secondary battery that the characteristics such as energy density of rechargeable nonaqueous electrolytic battery are significantly improved.
Background technology
As rechargeable nonaqueous electrolytic battery, that knows is to use alkali metal ion, the particularly lithium ion lithium ion battery as electrolyte ion (object cation).In the lithium ion battery of new generation that in batteries of electric automobile etc., uses, replace using all the time by LiMO
2The transition metal oxide (M represents transition elements) of expression is by LiMPO
4The phosphoric acid olivine compounds of expression receives publicity as positive active material of new generation.On the other hand, the main carbonaceous material such as graphite that uses in the negative pole.
But because the molecular weight of the phosphoric acid polyanion of this phosphoric acid olivine-type positive pole is bigger, so there is the limit in the theoretical capacity of battery (theoretical energy density, reversible capacity).For example, LiFePO
4Theoretical capacity be limiting condition when 170mAh/g.Use contains the higher anionic material of electronegativity as positive electrode, can access higher energy density in theory.Proposed to use positive active material (the Japanese kokai publication hei 9-22698 communique of metal fluoride before the inventor as rechargeable nonaqueous electrolytic battery; Japanese kokai publication hei 9-55201 communique).The theoretical energy density of these metal fluorides (reversible capacity) compares LiFePO
4Such olivine-type is anodal also high, for example, and FeF
3/ Li battery is assumed that the theoretical energy density (H.Arai etc., J.Power Sources, 68,716 pages (1997)) with about 240mAh/g.
Summary of the invention
In positive pole, use FeF
3In such metal fluoride, the rechargeable nonaqueous electrolytic battery of use carbonaceous material,, need to comprise object cations such as Na or Li in the positive pole in order to improve fail safe and energy density (capacity) as negative pole.But, do not have to find to prepare simply the method for this positive electrode with compound.
Therefore, other purpose of the present invention is, a kind of manufacture method of positive electrode active material for nonaqueous electrolyte secondary battery is provided, and it can access the cationic positive active materials of object such as comprising Na or Li in rechargeable nonaqueous electrolytic battery.
The inventor by making ad hoc structure alkali-metal fluoride and the fluoride generation force-chemical reaction of transition metal, the successfully synthetic Ca-Ti ore type fluorine class positive active material that contains Na or Li, thus finished the present invention.
That is a kind of mode of the present invention positive active material fluoride AM ' F of providing a kind of rechargeable nonaqueous electrolytic battery,
3And/or formula AM ' F
4The manufacture method of (A represents Na or Li, and M ' represents transition elements) is characterized in that, comprises following operation: the alkali metal fluoride and the formula M ' F of mutual-through type AF (A represents Na or Li) expression
2And/or M ' F
3The transition metal fluorides of (M ' expression transition elements) expression is carried out mechanical lapping and is handled production AM ' F
3And/or formula AM ' F
4The metal fluoride compound of expression.
In addition, according to the present invention, provide and contain the fluoride AM ' F that makes by said method
3And/or AM ' F
4The rechargeable nonaqueous electrolytic battery positive pole positive active material, contain the rechargeable nonaqueous electrolytic battery positive pole of this positive active material and have this positive pole and contain the rechargeable nonaqueous electrolytic battery of the negative pole of carbonaceous material.
On the other hand, because metal fluoride is an ionic compound, therefore think that it is dissolved in the polar solvent that contains in the electrolyte easily.Therefore, metal fluoride does not also reach the degree that is used for practical application as positive pole with active material.Therefore, think FeF
3Such metal fluoride is carrying out can stably using (F.Badway etc., J.Electrochem Soc.150, A1318 (2003)) with respect to polar solvent electrolyte after carbon coats.
Other purpose of the present invention is, the novel positive electrode active material for nonaqueous electrolyte secondary battery of performance metal fluoride speciality is provided.
The inventor finds, by with metal fluoride and the abundant mixing positive active material of making of carbonaceous material, can access the secondary cell with high-energy-density, thereby finish the present invention.
That is, another mode of the present invention provides a kind of positive electrode active material for nonaqueous electrolyte secondary battery, it is characterized in that, comprises the formula M F that coats with carbon
3The metal fluoride (M represents metallic element) of expression.
Description of drawings
Fig. 1 is the NaFeF synthetic according to first execution mode
3XRD spectra.
Fig. 2 is the NaMnF synthetic according to first execution mode
3XRD spectra.
Fig. 3 is the NaNiF synthetic according to first execution mode
3XRD spectra.
Fig. 4 is the section of structure of the structure of the rechargeable nonaqueous electrolytic battery that uses in the mensuration of expression battery behavior.
Fig. 5 represents the NaFeF with first execution mode
3Charging and discharging curve as the battery of positive active material.
Fig. 6 is the curve chart of the relation between ball mill incorporation time and the discharge capacity in the rechargeable nonaqueous electrolytic battery of expression second execution mode.
Fig. 7 A is the SEM photo of the sample that uses as positive active material of second execution mode.
Fig. 7 B is the EDS image of fluorine of the sample that uses as positive active material of second execution mode.
Fig. 7 C is the EDS image of carbon of the sample that uses as positive active material of second execution mode.
Fig. 8 is the figure of charging and discharging curve of the Li battery of the expression positive active material that uses second execution mode.
Fig. 9 is the figure of charging and discharging curve of the Na battery of the expression positive active material that uses second execution mode.
Figure 10 is the curve chart of multiplying power property of the Na battery of the expression positive active material that uses second execution mode.
Figure 11 is the dependent curve chart of depth of discharge of the Na battery of the expression positive active material that uses second execution mode.
Figure 12 is the curve chart of the relation between ball mill incorporation time and the discharge capacity in the rechargeable nonaqueous electrolytic battery of the expression positive active material that uses second execution mode.
Figure 13 is the figure of charging and discharging curve of the Li battery of the expression positive active material that uses second execution mode.
Figure 14 is the figure of charging and discharging curve of the Na battery of the expression positive active material that uses second execution mode.
Figure 15 A is the figure of charging and discharging curve of the rechargeable nonaqueous electrolytic battery of the expression positive active material that uses second execution mode.
Figure 15 B is the figure of charging and discharging curve of the rechargeable nonaqueous electrolytic battery of the expression positive active material that uses second execution mode.
Embodiment
First execution mode
First execution mode is described.
In the present embodiment, the alkali metal fluoride (A is Na or Li) and transition metal fluorides M ' F by formula AF is represented
2Or M ' F
3(M ' the expression transition elements) carry out the mechanical lapping processing, make Ca-Ti ore type fluorochemical AM ' F
3And/or AM ' F
4This fluoride AM ' F
3And/or AM ' F
4Positive active material contained in the positive pole as rechargeable nonaqueous electrolytic battery uses.At this, if this transition metal fluorides contain with transition metal be made as M ', by M ' F
2Or M ' F
3The compound of expression just can be used.Consider that from the viewpoint that the positive active material as rechargeable nonaqueous electrolytic battery uses this transition metal fluorides preferably comprises transition elements M ' for being selected from least a fluoride among V, Ti, Fe, Ni, Co or the Mn.That is, this transition metal fluorides preferably comprises VF
3, TiF
3, FeF
2, NiF
2, CoF
2Or MnF
2
Below in the explanation, at fluoride AM ' F
3And/or AM ' F
4Among, to generate AM ' F
3Situation be that example describes.The mechanical lapping of using in the present embodiment is handled, be by raw material is applied mechanical force, thus with the miniaturization of raw material physical property, the processing that makes raw material mechanically spread, make chemical reaction to carry out.This mechanical lapping is handled and is at room temperature carried out.In the present embodiment, think, generate the positive active material metal fluoride compd A M ' F of rechargeable nonaqueous electrolytic battery by following reaction
3
AF+M’F
2→AM’F
3
Be applicable to that the concrete grammar that mechanical lapping is handled is not particularly limited, can use pulverizing for solid matter, mixing and the whole bag of tricks that all the time uses.Be preferably ball milling as the mechanical lapping processing, be preferably the processing of using planetary ball mill (planetary ball milling) especially.Planetary ball mill possesses the mill main body of revolution and the ball grinder of rotation.Object being treated and crushing medium (being generally the minor diameter ball) are together put into the ball grinder of rotation.The centrifugal force that produces during by rotation, revolution makes the crushing medium motion, and object being treated is pulverized and mixing.Like this, use planetary ball mill raw material fully to be pulverized, to mix, consider preferred especially from this respect by the pulverizing that rotation, revolution motion carry out.
In the present embodiment, mechanical lapping is handled in the such atmosphere of inert gases of argon gas and is carried out with dry type.The condition that mechanical lapping is handled (for example the speed of processing time, pulverizing, mixing etc.), based on the result that obtains is analyzed, confirmed to product, the least possible and can generate target fluoride AM ' F as much as possible according to impurity (comprising residual raw material) by XRD (X-ray diffraction) etc.
3The mode of crystallization determine to get final product.Be noted that at this excessive mechanical lapping processing (for example the processing time is long) is for fluoride AM ' F
3The generation of crystallization is not preferred on the contrary.As an example, when using planetary ball mill, can adopt the condition of the about 150rpm～250rpm of rotational velocity of about 20 hours～about 30 hours processing time, ball grinder.
Use fluoride AM ' F
3During as positive active material, preferentially further carry out carbon and coat.Carbon coats and passes through fluoride AM ' F
3Carry out with the carbonaceous material mechanical mixture.When carrying out mechanical mixture, preferably use ball mill.In addition, especially preferably use planetary ball mill (planetary ballmilling).When using planetary ball mill, by the size reduction energy of rotation, revolution motion generation, with raw material metal fluoride MF
3Fully pulverize, mix with carbonaceous material.
Incorporation time is more than 4 hours, is generally 20～30 hours, but according to the combination of positive active material and carbonaceous material, also preferred sometimes short incorporation time (for example 4 hours).Be blended in the such atmosphere of inert gases of argon gas and carry out with dry type.
(electrode and battery)
In the present embodiment, what provide as above that operation obtains contains fluoride AM ' F
3Secondary cell (rechargeable nonaqueous electrolytic battery) positive active material, contain this positive active material anode of secondary battery and should positive pole and the rechargeable nonaqueous electrolytic battery that combines of negative pole.
In the present embodiment, anodal making for example can followingly be carried out: with fluoride AM ' F
3Powder and the binding material that uses as required, the electric conducting material that further uses as required mix, then the mixed-powder crimping on supporters such as stainless steel that obtains is shaped, or is filled in the metallic container.Perhaps, by with fluoride AM ' F
3Mixed-powder mix with organic solvent, the slurry that obtains is applied on the metal substrates such as aluminium, nickel, stainless steel, copper and also can obtains this positive pole.As this binding material, for example can enumerate: be selected from polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, propylene diene polymer, styrene butadiene rubbers, acrylonitrile-butadiene rubber, contain at least a material in fluorubber, polyvinyl acetate, polymethyl methacrylate, polyethylene and the nitrocellulose.In addition, as this electric conducting material, for example can enumerate: be selected from least a material in acetylene black, charcoal, graphite, native graphite, Delanium and the needle coke.In addition, as this organic solvent, can enumerate: be selected from least a organic solvent in N-methyl pyrrolidone, toluene, cyclohexane, dimethyl formamide, dimethylacetylamide, methylethylketone, methyl acetate, methyl acrylate, diethyl triamine, N-N-dimethylamino propylamine, oxirane, the oxolane.
In the rechargeable nonaqueous electrolytic battery of present embodiment, the negative electrode active material as the negative pole that is used in combination with above-mentioned positive pole can use sodium, lithium, these alkali-metal compounds, these alkali-metal alloys and carbonaceous material etc.But, in the present embodiment, be significant on as the negative electrode active material this point using carbonaceous material.As the carbonaceous material of negative electrode active material, preferred graphite-like material with carbon element in addition, also can use hard carbon that various polymer calcinings are obtained etc.But, be not limited to these.In addition, these carbonaceous materials can use in two or more mixing.
The making of negative pole gets final product according to known method, for example, can similarly make with the described method of positive pole.Promptly, for example the powder of negative electrode active material and the above-mentioned binding material that uses as required, the above-mentioned electric conducting material that further uses as required can be mixed, then this mixed-powder is configured as sheet, and it is crimped onto on the electric conductor nets (collector body) such as stainless steel, copper.In addition, also can be by for example this negative electrode active material being mixed with above-mentioned organic solvent with powder, the slurry that obtains is applied on the metal substrate such as copper and makes.
As other inscape of rechargeable nonaqueous electrolytic battery, can use the material that uses in the known rechargeable nonaqueous electrolytic battery.As other inscape, illustration is as follows.
Electrolyte comprises electrolyte and solvent usually.Solvent as electrolyte, as long as be that non-water system then is not particularly limited, for example can use at least a solvent that is selected from carbonates, ethers, ketone, sulfolane compounds, lactone, nitrile, chlorinated hydrocarbons, amine, ester class, amide-type and the phosphate compound.More specifically, can use as solvent and to be selected from 1, the 2-dimethoxy-ethane, 1, the 2-diethoxyethane, oxolane, the 2-methyltetrahydrofuran, ethylene carbonate, vinylene carbonate, methyl formate, methyl-sulfoxide, propylene carbonate, acetonitrile, gamma-butyrolacton, dimethyl formamide, dimethyl carbonate, diethyl carbonate, sulfolane, methyl ethyl carbonate, 1, the 4-diox, 4-methyl-2 pentanone, 1, the 3-dioxolanes, the 4-methyl isophthalic acid, the 3-dioxolanes, ether, sulfolane, methyl sulfolane, propionitrile, benzonitrile, butyronitrile, valeronitrile, 1, the 2-dichloroethanes, at least a solvent in trimethyl phosphate and the triethyl phosphate.In addition, also can use high imidazoles of oxidative resistance or quaternary amines ionic liquid as solvent.
As electrolyte, can use to be provided for making the material that carries out the alkali metal ion of electrochemical reaction between positive active material and the negative electrode active material.Particularly, can use and for example be selected from LiClO
4, LiPF
6, LiBF
4, LiCF
3SO
3, LiAsF
6, LiB (C
6H
5)
4, LiCl, LiBr, CH
3SO
3Li, CF
3SO
3Li, LiN (SO
2CF
3), LiN (SO
2C
2F
5)
2, LiC (SO
2CF
3)
3And LiN (SO
3CF
3)
2In at least a electrolyte substance.In addition,, also can use known solid electrolyte, for example have the LiTi of sodium superionic conductors (nasicon) structure as electrolyte
2(PO
4)
3Deng.
In the rechargeable nonaqueous electrolytic battery of present embodiment, can use existing known various materials, have no particular limits for battery key elements such as dividing plate, battery case, structural materials.The rechargeable nonaqueous electrolytic battery of present embodiment uses above-mentioned battery key element to assemble according to known method and gets final product.At this moment, also be not particularly limited for cell shapes, size.For example, can suitably adopt different shape, sizes such as cylindric, square, Coin shape.
In addition, more than in the explanation, at fluoride AM ' F
3And/or AM ' F
4In, to generate AM ' F
3Situation be that example is illustrated.For AM ' F
4, by with transition metal fluorides M ' F
2Replace to M ' F
3Can generate, can play when using and AM ' F as positive active material
3Identical effect.
Below, show feature of the present invention and put down in writing embodiment for further concrete, but the present invention and being not limited by the following examples.
(positive active material (the Ca-Ti ore type fluorine compounds AM ' F that contains Na
3) preparation)
With sodium fluoride (NaF) and transition metal fluorides M ' F
2(M ' be any of Fe, Ni, Mn) etc. molar mixture as raw material, use planetary ball mill to carry out mechanical lapping and handle.The purity of raw material is 99% purity, uses and light pure medicine company or add the raw material of river physics and chemistry company manufacturing.As planetary ball mill, use experiment to return translocation Port Star ト ミ Le with planetary rotary blender (experiment Yong Swam star) LP-4/2 (she makes made by rattan).Pack in the ball grinder of the 80ml ball of 2 diameter 20mm, 4 diameter 15mm and 15 diameter 10mm is again with pack into the ball of 3mm of the mode that adds up to 175g.Further charging feedstock in this ball grinder makes ball grinder be rotated with the rotational velocity of 200rpm.Processing time is set at 24 hours or 36 hours.
Fig. 1 represents with NaF and FeF
2The XRD spectra (CuK α) of the product that obtains for raw material.Among Fig. 1, the spectrogram by the product handling to obtain in 24 hours is with NaF+FeF
2(24 hours) expression.In addition, the spectrogram by the product handling to obtain in 36 hours is with NaF+FeF
2(36 hours) expression.In addition, among Fig. 1,, also shown NaFeF simultaneously in order to identify product
3, FeF
2Known spectrogram with NaF.As shown in Figure 1, the product of 24 hours product and 36 hours all and NaFeF
3Spectrogram height unanimity, confirm NaFeF
3Generation.In addition, as shown in Figure 1 as can be known, in the milled processed of 24 hours milled processed and 36 hours, the former impurity (residual raw material) is few, obtains the high product of crystallinity.
Fig. 2 represents with NaF and MnF
2The XRD spectra (CuK α) of the product that obtains for raw material.Same with Fig. 1, also shown NaMnF simultaneously
3, MnF
2Known spectrogram with NaF.As shown in Figure 2, confirm NaMnF
3Generation.
Fig. 3 represents with NaF and NiF
2The XRD spectra (CuK α) of the product that obtains for raw material.With Fig. 1,2 same, also shown NaNiF simultaneously
3, NiF
2Known spectrogram with NaF.As shown in Figure 3, confirm NaNiF
3Generation.
In addition, in Fig. 1～3, NaFeF
3, NaMnF
3And NaNiF
3Identify that respectively with spectrogram be the spectrogram (R.Hoppe etc., Z.Annorg.Allg.Chem.632,593 (2006)) of the spatial group Pnma that is the iris type of perovskite structure unit slight inclination.That is, the product that is obtained by present embodiment is accredited as the spatial group Pnma that is the iris type of perovskite structure unit slight inclination.
(mensuration of battery behavior)
To the NaFeF that synthesizes with embodiment 1
3(product of handling in 24 hours) estimated as the characteristic of the nonaqueous electrolyte battery of positive active material.
Fig. 4 is the schematic diagram of the structure of the rechargeable nonaqueous electrolytic battery that assembles of expression.This rechargeable nonaqueous electrolytic battery possesses positive pole 1, negative pole 2, anodal container 4, negative cover 5, dividing plate and electrolyte 3 (infiltration has the dividing plate of electrolyte 3).Positive pole 1 and negative pole 2 insert in the anodal container 4, accompany dividing plate between positive pole 1 and negative pole 2.
In order to make positive pole 1, positive active material, electric conducting material (acetylene black), binding material (PTFE) that embodiment 1 is made mix with 70: 25: 5 weight ratio, make particle.In addition, carry out the carbon coating, obtain anodal 1. in order to improve conductivity
Use sodium metal as negative pole 2.Use the NaClO of 1M
4/ PC is as electrolyte.Use polypropylene as dividing plate.
The rechargeable nonaqueous electrolytic battery that uses as above operation to make discharges and recharges mensuration (Na ガ ノ corporate system BST-2004).Condition determination is set at: temperature is 25 ℃, and current density is 0.2mA/cm
2Current density, voltage range is 1.5～4.0V, measures by CCV and carries out.Measurement result is shown in the upper semisection of Fig. 5.Among Fig. 5, solid line is represented the result of the 1st circulation, and dotted line is represented the result of the 2nd circulation.
In addition, be used for comparison, make not contain the FeF of Na
3Nonaqueous electrolyte battery (FeF as positive active material
3/ Na), under identical condition, carry out the mensuration of charge-discharge characteristic.FeF
3The lower semisection that the results are shown in Fig. 5 of/Na.
With NaFeF
3As the rechargeable nonaqueous electrolytic battery of positive active material, has initial stage discharge capacity at least about 90mAh/g.In addition, the 2nd time the circulation charging and discharging curve with FeF
3Cell height unanimity as positive active material.Be understood that thus according to present embodiment and do not lose its electro-chemical activity by the Na in the synthetic positive active material of mechanical lapping.That is, the positive active material that is understood that present embodiment can be used as the positive active material of rechargeable nonaqueous electrolytic battery.
Second execution mode
Then, second execution mode is described.The positive electrode active material for nonaqueous electrolyte secondary battery of present embodiment comprises the metal fluoride MF after carbon coats
3As this metal fluoride XF
3, can enumerate: the fluoride AM ' F shown in first execution mode
3The fluoride of (that is X=AM ') and 3 valency metals (below be designated as M) (below be designated as MF
3).
In the present embodiment, enumerate the fluoride MF that uses 3 valency metals
3The time example describe.
Metal fluoride MF
3In, as the metallic element shown in the M, so long as that the metal of 3 valencys then can use is any.As 3 valency metals shown in the M, for example can enumerate: Fe (iron), V (vanadium), Ti (titanium), Co (cobalt), Mn (manganese) etc.As the metal fluoride MF after the carbon coating
3, for example can enumerate: FeF
3, VF
3, TiF
3, CoF
3, MnF
3
Metal fluoride MF after this carbon coats
3The positive active material that contains in the positive pole as rechargeable nonaqueous electrolytic battery uses.As the negative electrode active material of the negative pole of this rechargeable nonaqueous electrolytic battery, can enumerate alkali metal or alkali metal compound.Preferred lithium (Li) or the sodium (Na) of using is as this negative electrode active material.Use the metal fluoride MF after this carbon coats
3As positive active material, use the rechargeable nonaqueous electrolytic battery of Li as negative electrode active material, demonstrate reversible charge-discharge characteristic capacious.In addition, do not use Li and when using Na, demonstrate reversible charge-discharge characteristic too as negative electrode active material.
For example, in lithium battery, use the FeF after carbon coats
3During as positive active material, can realize the reversible capacity (energy density) that 200mAh/g is above.In addition, in sode cell, if the metal fluoride MF after use carbon coats than lithium battery cheapness
3As positive active material, then obtain big reversible of energy density and discharge and recharge reaction (with reference to embodiment described later).
In the present embodiment, as this metal fluoride MF
3Particularly preferred compound is VF
3VF after coating with carbon
3In the lithium secondary battery as positive active material, charge characteristic and flash-over characteristic almost do not have difference.In addition, this lithium secondary battery is very efficient, has the high-energy-density (with reference to embodiment described later) above 200mAh/g.
As this metal fluoride MF
3, remove VF
3In addition, can also enumerate for example TiF
3, CoF
3, MnF
3Deng.At the TiF that uses after carbon coats
3, CoF
3And MnF
3In the lithium battery as positive active material, also have reversible charge-discharge characteristic and high-energy-density.Equally, the TiF after use carbon coats
3, CoF
3And MnF
3In the sode cell as positive active material, also have reversible charge-discharge characteristic and high-energy-density.
Metal fluoride XF after carbon in the present embodiment coats
3Make by will in atmosphere of inert gases, carrying out mechanical mixture with carbonaceous material as the metal fluoride reagent (add river physics and chemistry and learn Co., Ltd.'s system) of raw material.This metal fluoride reagent mixes with dry type with this carbonaceous material.
During with raw material metal fluoride reagent and carbonaceous material mechanical mixture, preferably use ball mill.In addition, especially preferably use planetary ball mill (planetary ball milling).When using planetary ball mill, by the size reduction energy of rotation, revolution motion generation, with raw material metal fluoride MF
3Fully pulverize, mix with carbonaceous material.
Incorporation time is more than 4 hours, is generally 20～30 hours, but according to the combination of positive active material and carbonaceous material, also preferred sometimes short incorporation time (for example 4 hours).Be blended in the such atmosphere of inert gases of argon gas and carry out with dry type.
As with raw material metal fluoride MF
3The carbonaceous material that mixes then can use any so long as have the carbon class material of conductivity.As this carbonaceous material, for example can enumerate: acetylene black, carbon black and active carbon etc.Metal fluoride MF
3Mixing ratio (metal fluoride MF with carbonaceous material
3: carbonaceous material) in weight basis, be preferably 50: 50～90: 10 scope, more preferably 70: 25.Metal fluoride MF
3Content at 50% when following of carbonaceous material, the electrochemical reaction between electrolyte and the positive active material is carried out insufficiently, can not obtain high reversible capacity.On the other hand, metal fluoride MF
3Content greater than 90% o'clock of carbonaceous material, carbon coats insufficient, the easy stripping of positive active material in electrolyte solution.
As mentioned above, by with raw material metal fluoride MF
3Mix in mechanical crushing with carbonaceous material, make metal fluoride MF
3Become the particle shape, metal fluoride MF
3The surface of particle is evenly coated by carbon.This confirms by the observation of using SEM (scanning electron microscopy) or EDS (beam split of energy dispersion X ray).
Because metal fluoride MF
3The surface of particle is evenly coated by carbon, therefore gives conductivity to above-mentioned positive active material.In addition, by coating, suppressed metal fluoride MF with carbon
3Stripping in non-aqueous electrolytic solution.Its result, the rechargeable nonaqueous electrolytic battery that obtains having high reversible capacity (energy density).
Below, in order further specifically to show feature of the present invention, put down in writing the various metal fluoride MF after coating with carbon
3As the lithium battery (Li battery) of positive active material with the various metal fluoride MF after the carbon coating
3The embodiment that discharges and recharges mensuration that carries out as the sode cell (Na battery) of positive active material.
(the metal fluoride MF after carbon coats
3Preparation)
(her rattan is made made, LA-P04) to metal fluoride FeF to use planetary ball mill
3And acetylene black (carbonaceous material) is carried out the mixing of stipulated time.Thus, obtain as anodal with the metal fluoride FeF after the carbon coating of active material
3The revolution of planetary ball mill is 200rpm.In addition, in enclosing, Ar atmosphere mixes.Mixing ratio (metal fluoride FeF
3: acetylene black: PTFE) be set at 70: 25: 5.Use the acetylene black of electrochemical industry manufacturing as acetylene black.Use the PTFE of ダ イ キ Application manufacturing as PTFE.Below, with the metal fluoride FeF after the resulting carbon coating
3Be designated as carbon and coat FeF
3
Use VF
3As metal fluoride MF
3, obtain the VF after carbon coats
3(below be designated as carbon and coat VF
3).In addition, remove use VF
3As metal fluoride MF
3In addition, other condition and carbon coat FeF
3Manufacturing conditions identical.
Use TiF
3As metal fluoride MF
3, obtain the TiF after carbon coats
3(below be designated as carbon and coat TiF
3).In addition, remove use TiF
3As metal fluoride MF
3In addition, other condition and carbon coat FeF
3Manufacturing conditions identical.
(structure of nonaqueous electrolyte battery, composition)
Then, assembling rechargeable nonaqueous electrolytic battery.As rechargeable nonaqueous electrolytic battery, make two kinds on Li battery and Na battery.Rechargeable nonaqueous electrolytic battery is a Coin shape rechargeable nonaqueous electrolytic battery shown in Figure 4.
As positive pole 1, the carbon that uses embodiment 3 to make respectively coats FeF
3, carbon coats VF
3Coat TiF with carbon
3Anodal 1 the coin that is shaped as diameter 1.0cm.
For the Li battery, use metal Li (this city metallic) as negative pole 2.The coin that is shaped as diameter 1.5cm of negative pole 2.In addition, use the LiPF of 1M
6/ EC: DMC (1: 1 volume %) (Fushan Mountain pharmaceutical industries system) is as electrolyte 3.Use the little porous body of polypropylene (セ Le ガ one De corporate system) as dividing plate.
For the Na battery, use metal Na (Aldrich K.K system) as negative pole 2.In addition, use the NaClO of 1M
4/ PC (Fushan Mountain pharmaceutical industries system) is as electrolyte 3.In addition, identical with the Li battery.
(discharging and recharging mensuration)
Then, respectively Li battery and the Na battery of making discharged and recharged mensuration.Measure the device that uses and be NAGANO BTS-2004 (the Na ガ ノ of Co., Ltd. system).Measuring temperature is 25 ℃, and voltage range is 2.0～4.5V (Li battery), 1.5～4.0V (Na battery), and current density is 0.2mA/cm in principle
2Carry out 2 cycle charge-discharges.
Embodiment 4
(carbon coats FeF
3)
Fig. 5 is the figure of the relation between the discharge capacity of expression incorporation time of planetary ball mill and rechargeable nonaqueous electrolytic battery.In the curve chart shown in Figure 6, shown with carbon to coat FeF
3Result's (solid line among the figure) of Li battery and coat FeF with carbon as anodal 1
3Result's (dotted line among the figure) of Na battery as anodal 1.In addition, be used for reference, also shown FeF
3Result's (hand mix) when passing through hand mix with carbonaceous material.As shown in Figure 2 as can be known, when using carbon to coat FeF
3The time, about more than 4 hours by incorporation time is set at, particularly about more than 10 hours, Li battery and Na battery all can access good discharge capacity.
Fig. 7 A～7C represents that the carbon that obtains with planetary ball mill mixing 24 hours coats FeF
3SEM photo and EDS photo.Fig. 7 A represents the SEM image, and Fig. 7 B represents the EDS image of F (fluorine), and Fig. 7 C represents the EDS image of C (carbon).The EDS image of F and the EDS image of C are corresponding well with the image of SEM, demonstrate the FeF as anodal 1
3The surface coat equably by carbon.
Fig. 8 represents to coat FeF with carbon
3Charging and discharging curve as the Li battery (lithium battery) of positive active material.Shown among Fig. 8 about mix result's (planetary ball mill 24 hours) of the positive active material of making in 24 hours by the use planetary ball mill.In addition, be used for comparison, the result's (hand mix) when having shown by hand mix.Among Fig. 8, solid line is represented the result of the 1st circulation, and dotted line is represented the result of the 2nd circulation.Hence one can see that, and the capacity of the Li battery of making under the manual case is less than 150mAh/g, and is relative therewith, uses carbon to coat FeF by planetary ball mill
3During as anodal 1 Li battery, obtain the above reversible capacity of 200mAh/g.
Fig. 9 represents to coat FeF with carbon
3Charging and discharging curve as the Na battery (sode cell) of positive active material.Same with Fig. 8, shown the carbon coating FeF that made in 24 hours about by using planetary ball mill to mix
3Result's (planetary ball mill 24 hours) and the result's (hand mix) when the hand mix.Among Fig. 9, solid line is represented the result of the 1st circulation, and dotted line is represented the result of the 2nd circulation.Hence one can see that, and the capacity of the Li battery of making under the manual case is less than 40mAh/g, and is relative therewith, using carbon to coat FeF
3During as anodal 1 Li battery, obtain the reversible capacity more than about 150mAh/g.Hence one can see that, coats FeF by using carbon
3, not only in the Li battery, and in the Na battery that with more cheap Na is negative pole, also can obtain high reversible capacity.
Figure 10 represents to use carbon to coat FeF
3The multiplying power property of sode cell as anodal 1.Among Figure 10, shown that respectively the current value in the time of will discharging and recharging is made as 0.2mA/cm
2, 1mA/cm
2, 2mA/cm
2And 5mA/cm
2The time the result.For example, current value is 0.2mA/cm
2The time, be about 20mAhg at capacity
-1～about 120mAhg
-1Scope in, cell voltage stabilizes to about 2.0V～about 2.5V.Thus, can confirm when keeping high reversible capacity, to present the scope of burning voltage.
Figure 11 represents to use carbon to coat FeF
3The depth of discharge dependence of Na battery as anodal 1.Transverse axis is represented discharge capacity, and the longitudinal axis is represented charging capacity.In addition, the dotted line among the figure is represented the line that discharge capacity equates with charging capacity.When current value is 60mAh/g, compare the line that discharge capacity and the ratio of charging capacity of the 2nd circulation more equates with charging capacity near discharge capacity with the 1st circulation.When current value is 90, also show same tendency during 120mAh/g.That is, hence one can see that, and along with the carrying out of charge and discharge cycles, efficiency for charge-discharge increases.
(carbon coats VF
3)
Figure 12 represents to use described carbon to coat VF
3As the relation between ball mill incorporation time and the discharge capacity in anodal 1 the Li battery.In addition, for coating VF with carbon
3Na battery as anodal 1 has shown the relation between ball mill incorporation time and the discharge capacity too.For the Na battery, when being 4 hours, the ball mill incorporation time obtains very good result.
Figure 13 represents to use carbon to coat VF
3The charging and discharging curve of Li battery as anodal 1.Among Figure 13, solid line is represented the result of the 1st circulation, and dotted line is represented the result of the 2nd circulation.As shown in figure 13, this Li battery has the above reversible capacity of 200mAh/g.And, minimum during charging with the difference of the cell voltage in when discharge, think battery very efficiently.
Figure 14 represents to use equally carbon to coat VF
3(the ball mill incorporation time is 4 hours) is as the charging and discharging curve of the Na battery of positive pole 1.Among Figure 14, solid line is represented the result of the 1st circulation, and dotted line is represented the result of the 2nd circulation.Described in the record relevant, coat VF by using the carbon that obtains through 4 hours ball mill incorporation time with Figure 12
3As positive active material, obtain the initial capacity of 160mAh/g, and obtain the reversible capacity of 140mAh/g.That is, obtain very good sode cell.
Embodiment 6
(carbon coats TiF
3)
Figure 15 A represents to use described carbon to coat TiF
3(ball mill incorporation time: 1 hour) is as the charging and discharging curve of the Li battery of positive pole 1.Among Figure 15 A, solid line is represented the result of the 1st circulation, and dotted line is represented the result of the 2nd circulation.In addition, Figure 15 B represents to use described carbon to coat TiF
3(ball mill incorporation time: 1 hour) is as the charging and discharging curve of the Na battery of positive pole 1.Among Figure 15 B, solid line is represented the result of the 1st circulation, and dotted line is represented the result of the 2nd circulation.Li battery and Na battery all have high reversible charge/discharge capacity to a certain degree.Think by using corresponding electrolyte, can realize higher reversible capacity.
The fluoride that will obtain according to the present invention anodal with combination such as carbon negative pole, can help thus safety, capacity greatly, the exploitation of rechargeable nonaqueous electrolytic battery cheaply.
The present invention can make the rechargeable nonaqueous electrolytic battery that comprises cheap Na battery realize high reversible charge/discharge capacity (energy density), positive active material of the present invention is expected to be used for the battery in industrial various fields, for example, need have the positive electrode of the bulk loads equilibrium of economy, fail safe and capacity concurrently with power supply or battery for electric automobile.
Claims (5)
1. the manufacture method of a positive electrode active material for nonaqueous electrolyte secondary battery wherein, possesses following operation:
Alkali metal fluoride that mutual-through type AF represents and formula M ' F
2And/or M ' F
3The transition metal fluorides of expression is carried out mechanical lapping and is handled production AM ' F
3And/or formula AM ' F
4The metal fluoride compound of expression, wherein, A represents Na or Li, M ' represents transition elements.
2. the manufacture method of positive electrode active material for nonaqueous electrolyte secondary battery as claimed in claim 1, wherein, described mechanical lapping is handled and is used planetary ball mill to carry out.
3. the manufacture method of positive electrode active material for nonaqueous electrolyte secondary battery as claimed in claim 1 or 2, wherein, described transition elements M ' is any among V, Ti, Fe, Ni, Co and the Mn.
4. the manufacture method of positive electrode active material for nonaqueous electrolyte secondary battery as claimed in claim 1 or 2 wherein, also possesses with carbon and coats described metal fluoride compd A M ' F
3And/or AM ' F
4Operation.
5. the manufacture method of positive electrode active material for nonaqueous electrolyte secondary battery as claimed in claim 4, wherein, the described operation that coats with carbon comprises: with described metal fluoride compd A M ' F
3And/or AM ' F
4The operation of in atmosphere of inert gases, carrying out mechanical crushing, mixing simultaneously with carbonaceous material with dry type.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006311126A JP2008130265A (en) | 2006-11-17 | 2006-11-17 | Surface coated metal fluoride electrode active material |
| JP311126/2006 | 2006-11-17 | ||
| JP2007083634A JP5091517B2 (en) | 2007-03-28 | 2007-03-28 | Fluoride cathode fabrication method |
| JP083634/2007 | 2007-03-28 | ||
| PCT/JP2007/072289 WO2008059961A1 (en) | 2006-11-17 | 2007-11-16 | Cathode active material for nonaqueous electrolyte secondary battery and method of producing cathode active material for nonaqueous electrolyte secondary battery |
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| Publication Number | Publication Date |
|---|---|
| CN101558518A CN101558518A (en) | 2009-10-14 |
| CN101558518B true CN101558518B (en) | 2011-09-14 |
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| JP2010170867A (en) * | 2009-01-23 | 2010-08-05 | Toyota Industries Corp | Positive electrode active material for nonaqueous secondary battery, and charge and discharge method of nonaqueous secondary battery |
| JP5359823B2 (en) * | 2009-11-30 | 2013-12-04 | 株式会社エクォス・リサーチ | Positive electrode active material and secondary battery using the same |
| RU2566085C1 (en) | 2011-08-29 | 2015-10-20 | Тойота Дзидося Кабусики Кайся | Active material for sodium accumulator positive electrode and method of its manufacturing |
| CN102299328B (en) * | 2011-08-31 | 2013-10-02 | 北京理工大学 | Metal fluoride cathode material of lithium secondary battery and preparation method of cathode material |
| JP5631346B2 (en) * | 2012-02-29 | 2014-11-26 | 三菱重工業株式会社 | Lithium ion secondary battery manufacturing method and lithium ion secondary battery |
| KR101703405B1 (en) | 2012-06-12 | 2017-02-06 | 도요타 지도샤（주） | Positive electrode material for sodium batteries and method for producing same |
| JP5877772B2 (en) * | 2012-08-23 | 2016-03-08 | 本田技研工業株式会社 | Cathode active material |
| JP2014060050A (en) | 2012-09-18 | 2014-04-03 | Honda Motor Co Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery |
| JP2014099395A (en) | 2012-10-16 | 2014-05-29 | Honda Motor Co Ltd | Positive electrode material |
| JP6081393B2 (en) | 2014-02-18 | 2017-02-15 | 本田技研工業株式会社 | Cathode active material |
| JP2015176656A (en) * | 2014-03-13 | 2015-10-05 | 本田技研工業株式会社 | positive electrode material |
| JP5966028B2 (en) * | 2014-03-19 | 2016-08-10 | 本田技研工業株式会社 | Positive electrode material for non-aqueous electrolyte secondary battery |
| CN104091949A (en) * | 2014-07-16 | 2014-10-08 | 北京化工大学常州先进材料研究院 | Charcoal-coated metal fluoride nano material with core-shell structure, preparation method and application of nano material as lithium battery positive electrode material |
| PL3311434T3 (en) * | 2015-06-19 | 2020-05-18 | Centre National De La Recherche Scientifique | Method for producing a positive electrode composite material for na ion battery |
| JP6502804B2 (en) * | 2015-09-10 | 2019-04-17 | トヨタ自動車株式会社 | Negative electrode current collector and fluoride ion battery |
| CN106981630B (en) * | 2016-01-19 | 2020-09-29 | 首尔大学校产学协力团 | Composite material of cathode material in secondary battery, preparation method and lithium secondary battery |
| JP6313345B2 (en) * | 2016-02-12 | 2018-04-18 | トヨタ自動車株式会社 | Active material and fluoride ion battery |
| CN107104248B (en) * | 2016-02-22 | 2019-06-11 | 中国科学院上海硅酸盐研究所 | A kind of potassium/sodium-ion battery is with opening frame fluoride positive electrode and preparation method thereof |
| CN105958043B (en) * | 2016-07-21 | 2018-10-09 | 广东工业大学 | A kind of doping Ti4+、Cr3+Borontrifluoride iron composite material and preparation method thereof, lithium ion battery |
| JP6705369B2 (en) * | 2016-12-22 | 2020-06-03 | トヨタ自動車株式会社 | Active material and fluoride ion battery |
| CN108336309B (en) * | 2017-01-20 | 2020-07-14 | 中国科学院上海硅酸盐研究所 | Perovskite open-frame iron-based fluoride positive electrode material and preparation method and application thereof |
| CN110832682B (en) * | 2017-06-30 | 2023-05-05 | 株式会社村田制作所 | Positive electrode active material for nonaqueous secondary battery and nonaqueous secondary battery using same |
| CN109980301A (en) * | 2017-12-28 | 2019-07-05 | 松下电器产业株式会社 | Fluoride ion conductor and fluoride ion secondary cell |
| JP7228776B2 (en) * | 2018-05-22 | 2023-02-27 | パナソニックＩｐマネジメント株式会社 | Active material for fluoride ion secondary battery, and fluoride ion secondary battery using the same |
| CN111029568A (en) * | 2019-11-01 | 2020-04-17 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of copper-based fluoride solid solution sodium ion battery positive electrode material |
| CN112909247A (en) * | 2021-01-21 | 2021-06-04 | 东北师范大学 | Zinc ion battery positive electrode material, preparation method and application thereof, and zinc ion battery |
| CN114335475B (en) * | 2021-12-31 | 2024-01-16 | 珠海冠宇电池股份有限公司 | Metal fluoride/porous carbon composite positive electrode material, positive electrode plate comprising same and battery |
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