CN1728421A - Li-mn-ni compound oxyde, its mfg.process and lithium secondary cell using the same - Google Patents
Li-mn-ni compound oxyde, its mfg.process and lithium secondary cell using the same Download PDFInfo
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- CN1728421A CN1728421A CNA2005100853575A CN200510085357A CN1728421A CN 1728421 A CN1728421 A CN 1728421A CN A2005100853575 A CNA2005100853575 A CN A2005100853575A CN 200510085357 A CN200510085357 A CN 200510085357A CN 1728421 A CN1728421 A CN 1728421A
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- C01—INORGANIC CHEMISTRY
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/48—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
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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
- H01M4/48—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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a manufacturing method for the lithium/manganese/nickel-based compound oxide, expressed by the general formula (1): Li<SB>x</SB>Mn<SB>1.5-y</SB>Ni<SB>0.5-z</SB>M<SB>y+z</SB>O<SB>4-w</SB>(wherein, 0.9<x<1.1, y>0, z>0, 0<y+z<0.1, and 0=<w<2; and M is at least one metal element selected from magnesium, aluminum, titanium and zirconium.), comprises the steps of baking a mixture containing lithium, manganese, nickel and an M at 950 to 1,050[deg.]C, cooling to obtain a precursor, and again baking the precursor at 550 to 650[deg.]C. The invention provides a lithium/manganese/nickel-based compound oxide that can be used for a lithium secondary cell which is excellent in charge/discharge cycle characteristics, and has a high Coulomb efficiency, a high discharge capacity maintenance rate and a high ratio of 5V discharge capacity range/(5V discharge capacity range+4V discharge capacity range).
Description
Technical field
The present invention relates to the manufacture method of Li-mn-ni compound oxyde.Very useful by the Li-mn-ni compound oxyde that manufacture method of the present invention obtains as the positive active material of lithium secondary battery.
Background technology
The applicant has formerly proposed as the manufacture method of the useful complex Li-Mn-oxide of the positive active material of lithium secondary battery (with reference to patent documentation 1 and 2).According to the complex Li-Mn-oxide that this manufacture method obtains, even contact with nonaqueous electrolytic solution, therefore the solution-off amount of manganese ion also seldom has the advantage of the preservation capacity characteristic that improves lithium secondary battery.But, use the lithium secondary battery of above-mentioned complex Li-Mn-oxide as positive active material, exist following such problem: when wanting to improve discharge capacity charging with the voltage that surpasses 4.3V, charge will descend significantly.
Therefore, in order to improve charge, the li-mn-ni compound oxide (with reference to patent documentation 3～5) that forms with a part of manganese in other the transition metal displacement complex Li-Mn-oxide such as nickel has been proposed.In these li-mn-ni compound oxides, use to have Li[Mn
3/2Ni
1/2] O
4The material of forming is as the lithium secondary battery of positive active material, has excellent charge, can produce the advantage of high voltage etc.
[patent documentation 1] spy opens the 2001-122626 communique
[patent documentation 2] spy opens the 2002-226213 communique
[patent documentation 3] spy opens the 2001-185148 communique
[patent documentation 4] spy opens the 2002-158007 communique
[patent documentation 5] spy opens the 2003-81637 communique
But, use the lithium secondary battery of existing Li-mn-ni compound oxyde as positive active material, the ratio in coulombic efficiency, discharge capacity sustainment rate and 5V discharge capacity zone/(5V discharge capacity zone+4V discharge capacity zone) is low, can not obtain the battery performance of being expected.
Summary of the invention
When therefore, the object of the present invention is to provide a kind of positive active material as lithium secondary battery to use, can form Li-mn-ni compound oxyde, its manufacture method of the high lithium secondary battery of the ratio in excellent charge and coulombic efficiency, discharge capacity sustainment rate and 5V discharge capacity zone/(5V discharge capacity zone+4V discharge capacity zone) and use its lithium secondary battery.
So, the inventor etc., the composite oxides that obtain changing initial feed and reaction temperature etc. have carried out deep research, found that: by the Li-mn-ni compound oxyde that uses the mixture to contain specific metallic element in specific temperature range, to fire to obtain for 2 times positive active material as lithium secondary battery, excellent charge, and can improve the ratio in coulombic efficiency, discharge capacity sustainment rate, 5V discharge capacity zone/(5V discharge capacity zone+4V discharge capacity zone), so far finish the present invention.
That is, the present invention is the manufacture method with the Li-mn-ni compound oxyde of following general formula (1) expression,
Li
xMn
1.5-yNi
0.5-zM
y+zO
4-w (1)
(in the formula, 0.9＜x＜1.1, y＞0, z＞0,0＜y+z＜0.1,0≤w＜2, M represents to be selected from least a metallic element in magnesium, aluminium, titanium and the zirconium.)
It is characterized in that: the mixture that will contain lithium, manganese, nickel and M is fired under 950～1050 ℃ of temperature, after cooling obtains precursor, fires this precursor again under 550～650 ℃ of temperature.
The manufacture method of Li-mn-ni compound oxyde of the present invention is characterized in that: the mixture that contains above-mentioned lithium, manganese, nickel and M is to be made of the complex chemical compound of lithium compound, manganese and nickel and the compound that contains M.
The manufacture method of Li-mn-ni compound oxyde of the present invention is characterized in that: the BET specific area of above-mentioned precursor is 0.2～0.6m
2/ g.
The manufacture method of Li-mn-ni compound oxyde of the present invention is characterized in that: the average grain diameter of above-mentioned precursor is 5～15 μ m.
The manufacture method of Li-mn-ni compound oxyde of the present invention is characterized in that: above-mentioned M is magnesium or titanium.
Li-mn-ni compound oxyde of the present invention is characterized in that: by the said method manufacturing.
Lithium secondary battery of the present invention is characterized in that: possess the positive pole that contains above-mentioned Li-mn-ni compound oxyde.
In the present invention, in the formula of above-mentioned li-mn-ni compound oxide, the error range of the mol ratio 1.5 of Mn is ± 0.05, the error range of the mol ratio 0.5 of Ni is ± and 0.05.
The invention effect
The Li-mn-ni compound oxyde of the high lithium secondary battery of a kind of ratio that can form excellent charge and coulombic efficiency, discharge capacity sustainment rate and 5V discharge capacity zone/(5V discharge capacity zone+4V discharge capacity zone) can be provided according to the present invention.
Description of drawings
Fig. 1 represents to use the composite oxides that obtain among the embodiment 1 initial stage discharge capacity curve chart as the lithium secondary battery of positive active material.
Fig. 2 represents to use the composite oxides that obtain among the embodiment 2 initial stage discharge capacity curve chart as the lithium secondary battery of positive active material.
Fig. 3 represents to use the composite oxides that obtain among the embodiment 3 initial stage discharge capacity curve chart as the lithium secondary battery of positive active material.
Fig. 4 represents to use the composite oxides that obtain in the comparative example 1 initial stage discharge capacity curve chart as the lithium secondary battery of positive active material.
Embodiment
Below, based on preferred implementation of the present invention the present invention is described.
Li-mn-ni compound oxyde by manufacturing of the present invention is the spinel oxides of representing with following general formula (1).
Li
xMn
1.5-yNi
0.5-zM
y+zO
4-w (1)
(in the formula, 0.9＜x＜1.1, y＞0, z＞0,0＜y+z＜0.1,0≤w＜2, M represents to be selected from least a metallic element in magnesium, aluminium, titanium and the zirconium.)
This lithium manganese nickel class fluorine composite oxide is made by the method that comprises following operation, promptly, the mixture that will contain lithium, manganese, nickel and M is fired under 950～1050 ℃ of temperature, obtain after the cooling precursor operation (below, be called first ablating work procedure), the precursor that will obtain in first ablating work procedure is the operation of firing again under 550～650 ℃ of temperature (below, be called second ablating work procedure).
The initial feed of using among the present invention is the mixture that contains lithium, manganese, nickel and M.As the mixture of this initial feed, can enumerate following such material, can therefrom select arbitrarily.
(1) complex chemical compound of manganese and nickel, lithium compound and contain the formed mixture of compound of M.
(2) manganese compound, nickel compound, lithium compound and contain the formed mixture of compound of M.
As manganese in above-mentioned (1) and nickel class complex chemical compound, for example can enumerate the complex hydroxide of manganese and nickel, compound alkali formula hydroxide, compound carbonate, composite oxides, can use these materials are two or more alone or in combination.More particularly, above-mentioned complex hydroxide and compound alkali formula hydroxide can be made up and use.Particularly, among these complex chemical compounds, preferably use complex hydroxide or compound alkali formula hydroxide from suppressing the viewpoint of accessory substance.In addition, in these complex chemical compounds, the atomic ratio of manganese and nickel is preferably Mn: Ni=72.5: 27.5～77.5: 22.5, and Mn: Ni=75 more preferably: 25.When the ratio of manganese was very few, the discharge capacity of the per unit weight of positive active material can reduce, and when the ratio of nickel was very few, 4V discharge capacity zone (discharge of not expecting) increased.
Above-mentioned complex chemical compound for example can be modulated by coprecipitation.More particularly, complex hydroxide can mix, make the complex hydroxide co-precipitation to modulate by the mixed aqueous solution that will contain manganese compound and nickel compound, the aqueous solution of complexing agent and the aqueous solution of alkali.At this moment, the manganese compound in the mixed aqueous solution and the mixed proportion of nickel compound be, makes the manganese in the resulting complex hydroxide and the atomic ratio of nickel be preferably Mn: Ni=72.5: 27.5～77.5: 22.5, Mn: Ni=75 more preferably: 25.
As employed manganese compound here, for example can enumerate the water soluble salt of manganese such as manganese sulfate, manganese nitrate, manganese chloride.As nickel compound, for example can enumerate the water soluble salt of nickel such as nickelous sulfate, nickel nitrate, nickel chloride.
As complexing agent, use can form the complexing agent of the complexing body of manganese and nickel.For example can enumerate ammonium ion source (ammonia, ammonium chloride, ammonium carbonate, ammonium fluoride), hydrazine, edetate, glycine etc.
In co-precipitation operation, the pH value of reactant liquor maintains in the scope about 9～13.Keeping of pH value, the aqueous solution that for example can add alkali such as NaOH or potassium hydroxide carries out.
In addition, as other method of modulation complex hydroxide, for example can use the spy to open the method for putting down in writing in the 2002-201028 communique.More particularly, in reactive tank, stir fully, simultaneously, in the ambiance of inert gas or reducing agent in the presence of, supply with nickel salt aqueous solution and complexing agent and the alkali metal hydroxide that contains cobalt salt (cobalt (II) ion) and manganese salt (manganese (II) ion) continuously, its continuous crystallisation is grown up, take out resulting sediment continuously, can modulate thus.
Preferably make salinity in the reactive tank remain in the scope of 50～200mS/cm ± 5mS/cm, ammonium concentration is remained in the scope of 1～10g/L ± 0.5g/L.In addition, preferably make reaction pH value remain in 11.0～13.0 ± 0.05 the scope, reaction temperature is remained in 25～80 ℃ ± 0.5 ℃ the scope.As the conditioning agent of salinity, can enumerate sodium chloride, potassium chloride, sodium sulphate, potassium sulfate, hydrochloric acid ammonium, ammonium sulfate etc.As calcium salt, can enumerate nitrate, acetate or oxalates etc.
In addition, compound alkali formula hydroxide is modulated by following method,, obtains the post precipitation of complex hydroxide according to the method described above that is, is blown into air in reactant liquor, with the complex hydroxide oxidation.
Composite oxides are modulated by following method,, obtain the post precipitation of complex hydroxide according to the method described above that is, for example under 200～500 ℃ of temperature it are carried out heat treated.
Compound carbonate can be modulated by following method, that is, will contain the mixed aqueous solution of manganese compound and nickel compound, the aqueous solution of complexing agent and the aqueous solution of carbonic acid alkali metal salt or bicarbonate alkali metal salt and mix, and makes the compound carbonate co-precipitation.In addition, by in above-mentioned mixed aqueous solution, importing carbon dioxide gas, also can modulate compound carbonate.At this moment, the manganese compound in the mixed aqueous solution and the mixed proportion of nickel compound be, makes the manganese in the resulting compound carbonate and the atomic ratio of nickel be preferably Mn: Ni=72.5: 27.5～77.5: 22.5, Mn: Ni=75 more preferably: 25.As employed carbonic acid alkali metal salt or bicarbonate alkali metal salt here, for example can enumerate sodium carbonate, potash, sodium acid carbonate etc.
On the other hand,, for example can enumerate oxide, hydroxide, alkali formula hydroxide, the carbonate of manganese, they can be used separately or are used in combination as the manganese compound in above-mentioned (2).As nickel compound, for example can enumerate oxide, hydroxide, alkali formula hydroxide, the carbonate of nickel, they can be used separately or are used in combination.But preferred manganese compound and nickel compound use of the same race.For example, when using oxide, preferably also use oxide as nickel compound as manganese compound.Particularly preferred combination is the combination of manganese dioxide and nickel oxide.
As the lithium compound that uses in (1) and (2), for example can enumerate lithium carbonate, lithium hydroxide, lithium nitrate, lithia, wherein and since industrial obtain easily and price cheap, so preferred lithium carbonate.
In addition, (1) reaches the compound that contains M that uses in (2), be to contain the compound that is selected from least a metallic element in magnesium, ammonium, titanium and the zirconium, the concrete compound that contains M, can enumerate oxide, carbonate, acylate of M etc., they can be used or make up two or more uses separately.
For these compounds, no matter its manufacture process, but in order to make highly purified Li-mn-ni compound oxyde, preferred foreign material amount will lack.In addition, in order to improve reactivity, preferably use fine compound, in most cases, the average grain diameter of being tried to achieve by laser method particle size distribution method is 5～15 μ m, is preferably 8～12 μ m.If the average grain diameter of compound then can obtain the homodisperse mixture of compound in above-mentioned scope, can obtain utilizing X-ray diffraction to be determined as single-phase Li-mn-ni compound oxyde thus, be preferred therefore.
In manufacture method of the present invention, use the mixture of (1) as initial feed, in using the lithium secondary battery of Li-mn-ni compound oxyde as positive active material, owing to can obtain higher discharge capacity and favorable charge-discharge cycle characteristics, so be preferred.
In manufacture method of the present invention, at first, complex chemical compound, the lithium compound of (1) manganese and nickel and the compound that contains compound or (2) manganese compound, nickel compound, the lithium compound of M and contain M are mixed, obtain the homodisperse mixture of these compounds.This mixes, with the arbitrary method among dry type or the wet type all can owing to make easily, so preferred dry.
The cooperation ratio of each compound in the said mixture is, the mol ratio of Li/ (Mn+Ni+M) is 0.45～0.55, is preferably 0.495～0.505, is preferably as far as possible the value near the ratio 0.5 of the theoretical amount that can access spinel structure especially.In addition, the mol ratio of M/ (Mn+Ni) is 0.0005～0.05, is preferably 0.001～0.025.Its reason is: if than 0.0005 little, the compound additive effect that then contains M is not obvious, and on the other hand, if surpass 0.05, the compound additive effect that then contains M is not only saturated, also has the tendency that discharge capacity reduces.
Below, first ablating work procedure is described.
In first ablating work procedure, the mixture that will contain lithium, manganese, nickel and M 950～1050 ℃, be preferably 975～1025 ℃, more preferably fire under 975～1000 ℃ of temperature.First ablating work procedure carries out in atmosphere usually.Fire by this, this mixture is converted into precursor.The composition of this precursor is identical with the Li-mn-ni compound oxyde of the spinel-type of representing with general formula (1), in the present invention, the Li-mn-ni compound oxyde that obtains in this first ablating work procedure is called precursor, in order that with second ablating work procedure described later in the Li-mn-ni compound oxyde difference that obtains.
In this first ablating work procedure, the reason that firing temperature is set in the above-mentioned scope is: in the time of discontented 950 ℃, though charge is good, the solution-off amount of manganese sharply increases, and on the other hand, when surpassing 1050 ℃, charge can reduce.In addition, programming rate in first ablating work procedure and cooling rate are preferably 30 ℃/h～300 ℃/h.During the discontented 30 ℃/h of programming rate and cooling rate, make efficient and might reduce, when surpassing 300 ℃/h, not only be difficult to the battery performance that obtains expecting, and be easy to generate the division of firing alms bowl (stove) etc.
In first ablating work procedure, control the specific area of resulting precursor, obtain the few Li-mn-ni compound oxyde of manganese solution-off amount aspect on be favourable.Specifically, initial feed, that is, lithium, manganese, nickel and contain the BET specific area of the mixture of M are generally 10～15m
2/ g fires it in the said temperature scope, the BET specific area of preferred precursor is 0.2～0.6m
2/ g, more preferably 0.2～0.4m
2/ g.For the precursor of the BET specific area that obtains having such scope, under the temperature in above-mentioned scope, adjust the firing time aptly to get final product, more particularly, the firing time is 8～30 hours, is preferably 12～20 hours especially.
And, above-mentioned precursor, except the BET specific area, the average grain diameter of being tried to achieve by laser method particle size distribution method is preferably 5～15 μ m, more preferably 8～12 μ m.If the average grain diameter of precursor in above-mentioned scope, can enter the scope of suitable electrode density, TAP density and specific area, and can improve the battery performance of charge etc., be particularly preferred therefore.For the precursor of the average grain diameter that obtains having such scope, use initial feed in the scope of above-mentioned average grain diameter, at above-mentioned firing temperature and react in the firing time and get final product.
Temporarily cool off at this resulting precursor.Chilling temperature is set at below 50 ℃, for easy and cool to room temperature.
Below, second ablating work procedure is described.
In second ablating work procedure, 550～650 ℃, be preferably under 600～650 ℃ of temperature and fire the precursor that obtains in first ablating work procedure.Compare with the precursor that obtains in first ablating work procedure, fire by this, reduced the solution-off amount of manganese, in addition, in using the lithium secondary battery of resulting Li-mn-ni compound oxyde, can improve the ratio in 5V discharge capacity zone/(5V discharge capacity zone+4V discharge capacity zone) as positive active material.Its reason can be thought: repair the structure of the anoxic in the spinelle, will think that the manganic of solution-off reason changes the tetravalence manganese that is difficult to solution-off into.In addition, because manganic is converted into tetravalence manganese, promoted coulombic efficiency.That is, irreversible capacity diminishes.
The reason that firing temperature is set at above-mentioned scope in this second ablating work procedure is: discontented 550 ℃ or when surpassing 650 ℃, the manganic that forms the 4V region of discharge is difficult to be converted into the tetravalence manganese that forms the 5V region of discharge, can make the ratio that exists of 4V region of discharge increase.In addition, programming rate in second ablating work procedure and cooling rate are preferably 30 ℃/h～300 ℃/h.During the discontented 30 ℃/h of programming rate and cooling rate, might reduce manufacturing efficient, when surpassing 300 ℃/h, not only be difficult to the battery performance that obtains expecting, and be easy to generate the division of baking furnace (alms bowl).
This second ablating work procedure carries out in atmosphere usually, perhaps carries out in oxygen concentration is oxygen ambiance more than the 20wt%.Firing time is set at the time that can fully repair the anoxic structure in the spinelle, and is long more effective more, but considers the repairing of anoxic structure and the balance of manufacturing efficient, is preferably 10～100 hours, more preferably 15～50 hours.
After firing end, cool off, pulverize as required, screen, obtain Li-mn-ni compound oxyde with general formula (1) expression as object.
The preferred rerum natura of this Li-mn-ni compound oxyde, from reducing the viewpoint of manganese solution-off amount, the BET specific area is preferably 0.2～0.6m
2/ g is preferably 0.2～0.4m especially
2/ g.In addition, with regard to Li-mn-ni compound oxyde, from the viewpoint of electrode density and TAP density and then battery performance, the average grain diameter of being tried to achieve by laser method particle size distribution method is preferably 5～15 μ m, is preferably 8～12 μ m especially.
The Li-mn-ni compound oxyde that obtains thus, the solution-off amount of its manganese reduces, and uses particularly useful as positive active material in lithium secondary battery.Therefore, under the situation that the positive active material that uses this Li-mn-ni compound oxyde as lithium secondary battery uses, can provide the high lithium secondary battery of ratio in a kind of excellent charge and coulombic efficiency, discharge capacity sustainment rate and 5V discharge capacity zone/(5V discharge capacity zone+4V discharge capacity zone).Particularly, when using magnesium as the M in the general formula (1), above-mentioned effect further improves, and is preferred therefore.
Lithium secondary battery has positive pole, negative pole, barrier film and contains the nonaqueous electrolytic solution of lithium salts.Positive pole is for example to apply anode mixture, dry back formed on positive electrode collector.Anode mixture contains positive active material, conductive agent, adhesive that is made of the Li-mn-ni compound oxyde that utilizes manufacture method of the present invention to obtain and the filler that adds as required.
As positive electrode collector, so long as in the battery that is constituted, can not cause the electrical conductivity body of chemical change, just be not particularly limited, for example can enumerate stainless steel, nickel, aluminium, titanium, fire carbon, utilize carbon, nickel, titanium, silver carries out surface treatment to aluminium or stainless surface and the material that obtains etc.
As conductive agent, for example can enumerate graphite, carbon black, acetylene carbon black, carbon fiber or conductive materials such as metal, nickel powder such as native graphite and electrographite.As native graphite, for example can enumerate flaky graphite, flaky graphite and amorphous graphite etc., they can use separately also can make up two or more uses.The cooperation ratio of conductive agent in anode mixture, is 1～50 weight %, is preferably 2～30 weight %.
As adhesive; for example can enumerate Kynoar, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinylpyrrolidone, ethylene-propylene-diene terpolymers (EPDM), sulfonated epdm, styrene butadiene rubbers, fluorubber, poly(ethylene oxide) etc. polysaccharide, thermoplastic resin, have the polymer of caoutchouc elasticity etc., can use a kind of in them or be used in combination more than two kinds.The cooperation ratio of adhesive in anode mixture, is 2～30 weight %, is preferably 5～15 weight %.
Filler is the material that is used to suppress anodal volumetric expansion etc. in anode mixture, adds as required.As filler, so long as in the battery that is constituted, can not cause the fibrous material of chemical change, can use, for example can use the fiber of olefin polymers such as polypropylene, polyethylene, glass, carbon etc.The addition of filler is not particularly limited, and is preferably 0～30 weight % in anode mixture.
Negative pole is for example by applying negative material on negative electrode collector, carrying out drying then and form.As negative electrode collector, so long as in the battery that is constituted, can not cause the electrical conductivity body of chemical change, just be not particularly limited, for example can enumerate stainless steel, nickel, copper, titanium, aluminium, fire carbon, utilize carbon, nickel, titanium, silver carries out surface treatment to copper or stainless surface and the material that obtains and aluminium-cadmium alloy etc.
As negative material, be not particularly limited, for example can enumerate carbonaceous material, composite oxide of metal, lithium metal, lithium alloy etc.As carbonaceous material, for example can enumerate difficult graphitized carbon material, graphite is material with carbon element etc.As composite oxide of metal, for example can enumerate Sn
pM
1 1-pM
2 qO
r(in the formula, M
1Expression is selected from more than one the element among Mn, Fe, Pb and the Ge, M
2Expression is selected from more than one the element in Al, B, P, Si, periodic table the 1st family, the 2nd family, the 3rd family and the halogen element, 0＜p≤1,1≤q≤3,1≤r≤8) etc. compound.
As barrier film, can use the insulating properties film that has big ion permeability, has the mechanical strength of regulation.From organic solvent resistance and hydrophobicity, can use the olefin polymer of polypropylene etc. or thin slice or the nonwoven fabrics that glass fibre or polyethylene etc. are made.As the aperture of barrier film, as long as in common scope, for example be 0.01～10 μ m as battery applications.As the thickness of barrier film, need only the scope of using at common battery, for example be 5～300 μ m.In addition, the solid electrolyte that uses polymer etc. as electrolytical situation described later under, solid electrolyte can the double as barrier film.In addition, in order to improve discharge or charge characteristic, can in electrolyte, add the compound of pyridine, triethyl phosphorite, triethanolamine etc.
The nonaqueous electrolyte that contains lithium salts is made of nonaqueous electrolyte and lithium salts.As nonaqueous electrolyte, can use nonaqueous electrolytic solution or organic solid electrolyte based.As nonaqueous electrolytic solution, for example can enumerate the N-N-methyl-2-2-pyrrolidone N-, propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, the 2-dimethoxy-ethane, the tetrahydroxy furans, the 2-methyltetrahydrofuran, dimethyl sulfoxide (DMSO), 1,3-two oxa-s penta ring, formamide, dimethyl formamide, two oxa-s, penta ring, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, two oxa-s, penta ring derivatives, sulfolane, 3-methyl-2-oxazolidone, the propylene carbonate ester derivant, tetrahydrofuran derivatives, diethyl ether, 1,3-propane sultone etc. be the solvent of one or more mixing of organic solvent inert to proton.
As organic solid electrolyte based, for example can enumerate polythene derivative or contain its polymer, polypropylene oxide derivative or contain its polymer, phosphate ester polymer etc.As lithium salts, can use the lithium salts that is dissolved in the above-mentioned nonaqueous electrolyte, for example can enumerate LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiCF
3CO
2, LiAsF
6, LiSbF
6, LiB
10Cl
10, LiAlCl
4, chloromethane borine lithium, lower aliphatic carboxylic acid lithium, tetraphenyl lithium borate etc. the salt of one or more mixing.
The shape of battery can be any one in the shapes such as button shape, sheet, cylindrical shape, square.The purposes of lithium secondary battery of the present invention, be not particularly limited, for example can enumerate consumer electronic devices such as electronic equipment, automobile, electric motor car, game machine such as notebook computer, portable minisize PC, pocket word processor, mobile phone, radio apparatus, portable CD-audio player, radio receiver.
Embodiment
Below enumerate embodiment and specify the present invention, but the present invention is not limited to these embodiment.
[modulation of the composite oxides of manganese and nickel]
Prepared the NiSO of the 0.4mol/L of 300ml
46H
2The MnSO of O and 1.2mol/L
45H
2The mixed-salt aqueous solution of O (Capacity Ratio is 1: 1).In addition, prepare the aqueous solution 200mL of NaOH of the ammonia spirit 100mL of 1.5mol/L and 6mol/L again as complexing agent.This three's the aqueous solution splashes in the beaker of the 1L capacity that has added 200mL water simultaneously.In splashing into operation, adjust the speed that splashes into of each aqueous solution, make that the pH value of reactant liquor is 11.The speed that splashes into is respectively that mixed-salt aqueous solution is that 60mL/min, ammonia spirit are that 20mL/min, the NaOH aqueous solution are 40mL/min.Reactant liquor remains on 50 ℃.Make the hydroxide co-precipitation of Mn and Ni thus.Stir 9 hours coprecipitates and slaking.Therebetween, with the amount of liquid in the mode inhibitory reaction system of overflow, the liquid of exchange overflow in per 3 hours.The hydroxide that utilizes pulp washing and precipitating again to generate after the filtration.Judge cleaning performance with conductivity meter, clean fully.After the drying, utilize X-ray diffraction method to precipitate the analysis of product.Consequently can confirm: the precipitation product is not a noncrystalline, is Mn after the mutual solid solution of Mn and Ni and the cocrystallization body of Ni, and it forms available basically Mn
0.75Ni
0.25(OH)
2Represent.The BET specific area of this precipitation product is 12.2m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 9.7 μ m.
[embodiment 1]
The modulation of＜initial feed 〉
The composite oxides of above-mentioned resulting manganese of weighing and nickel, lithium carbonate (Japanese chemical industry society system, average grain diameter 14 μ m) and MgO (the マ テ リ ア of space portion Le ズ society system, average grain diameter 1 μ m), make it become Li: Mn: Ni: the Mg mol ratio is 0.5: 0.75: 0.25: 0.005, then, utilize mixing and blending machine evenly to mix, obtain the mixture that contains Li, Mn, Ni and Mg as initial feed.
＜the first ablating work procedure 〉
Below, resulting mixture was fired 12 hours in atmosphere, under 1000 ℃ of temperature, obtained precursor.Reaching maximum temperature band programming rate before is 100 ℃/h.With cooling rate be 100 ℃/h naturally cool to room temperature (20 ℃) thereafter.After the cooling, with the broken precursor of home-use mixer calomel mercurous chloride.The BET specific area of precursor is 0.39m
2/ g, the average grain diameter of trying to achieve with laser method particle size distribution method is 10.5 μ m.
＜the second ablating work procedure 〉
With the precursor that obtains in first ablating work procedure, the system of reburning is 15 hours in atmosphere, under 600 ℃ of temperature.Reaching maximum temperature band programming rate before is 100 ℃/h.After firing, be 100 ℃/h cool to room temperature (20 ℃), then, pulverize, screen, obtain using composition formula Li with cooling rate
1.000Mn
1.4925Ni
0.4975Mg
0.01O
3.9925The Li-mn-ni compound oxyde of expression.The BET specific area of these composite oxides is 0.38m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 10.6 μ m.
In addition, main modulation condition is as shown in table 1, and the various rerum naturas of resulting Li-mn-ni compound oxyde are as shown in table 2.
[embodiment 2]
Except the firing temperature with first ablating work procedure is made as 950 ℃, other is identical with embodiment 1, obtains using composition formula Li
1.000Mn
1.4925Ni
0.4975Mg
0.01O
3.9925The Li-mn-ni compound oxyde of expression.The BET specific area of these composite oxides is 0.46m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 10.4 μ m.
In addition, the BET specific area of precursor is 0.48m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 10.5 μ m.
In addition, main modulation condition is as shown in table 1, and the various rerum naturas of resulting Li-mn-ni compound oxyde are as shown in table 2.
[embodiment 3]
Except using TiO
2(clear and electrician society system, average grain diameter are 0.5 μ m) replace MgO, make Li in the initial feed: the mol ratio of Mn: Ni: Ti is 0.5: 0.75: 0.25: beyond 0.005, other is identical with embodiment 1, obtains using composition formula Li
1.000Mn
1.4925Ni
0.4975Ti
0.01O
3.9925The Li-mn-ni compound oxyde of expression.The BET specific area of these composite oxides is 0.37m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 10.9 μ m.
In addition, main modulation condition is as shown in table 1, and the various rerum naturas of resulting Li-mn-ni compound oxyde are as shown in table 2.
[embodiment 4]
Except making Li: the mol ratio of Mn: Ni: Mg is 0.475: 0.75: 0.25: 0.005 modulates the initial feed, and other is identical with embodiment 1, obtains using composition formula Li
0.95Mn
1.4925Ni
0.4975Mg
0.01O
3.9925The Li-mn-ni compound oxyde of expression.The BET specific area of these composite oxides is 0.40m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 10.6 μ m.
In addition, the various rerum naturas of resulting Li-mn-ni compound oxyde are as shown in table 2.
[embodiment 5]
Except making Li: the mol ratio of Mn: Ni: Mg is 0.525: 0.75: 0.25: 0.005 modulates the initial feed, and other is identical with embodiment 1, obtains using composition formula Li
1.05Mn
1.4925Ni
0.4975Mg
0.01O
3.9925The Li-mn-ni compound oxyde of expression.The BET specific area of these composite oxides is 0.38m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 10.3 μ m.
In addition, the various rerum naturas of resulting Li-mn-ni compound oxyde are as shown in table 2.
[embodiment 6]
Weighing lithium carbonate (Japanese chemical industry society system, average grain diameter are 14 μ m), manganese dioxide (pure chemical society system, average grain diameter are 5 μ m), nickel oxide (with the pure medicine of light society system, average grain diameter be 7 μ m) and MgO (the マ テ リ ア of space portion Le ズ society system, average grain diameter are 1 μ m), make that the mol ratio of Li: Mn: Ni: Mg is 0.5: 0.75: 0.25: 0.005, then, evenly mix with mixing and blending machine, obtain the mixture that contains Li, Mn, Ni and Mg as initial feed, in addition, identical with embodiment 1, obtain using composition formula Li
1.000Mn
1.4925Ni
0.4975Mg
0.01O
3.9925The Li-mn-ni compound oxyde of expression.The BET specific area of these composite oxides is 0.48m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 8.2 μ m.
In addition, the various rerum naturas of resulting Li-mn-ni compound oxyde are as shown in table 2.
[comparative example 1]
The modulation of＜initial feed 〉
The used identical manganese and the composite oxides and the lithium carbonate (average grain diameter is 14 μ m) of nickel among weighing and the embodiment 1, make that the mol ratio of Li: Mn: Ni is 0.5: 0.75: 0.25, then, evenly mix with mixing and blending machine, obtain the mixture that contains Li, Mn and Ni as initial feed.
＜the first ablating work procedure 〉
Then, resulting mixture was fired 12 hours in atmosphere, under 1000 ℃ of temperature, obtained precursor.Reaching maximum temperature band programming rate before is 100 ℃/h.With cooling rate be 100 ℃/h naturally cool to room temperature (20 ℃) thereafter.After the cooling, with the broken precursor of home-use mixer calomel mercurous chloride.The BET specific area of precursor is 0.41m
2/ g, the average grain diameter of trying to achieve with laser method particle size distribution method is 10.8 μ m.
＜the second ablating work procedure 〉
With the precursor that obtains in first ablating work procedure, in atmosphere, under 600 ℃ of temperature, fired 15 hours.Reaching maximum temperature band programming rate before is 100 ℃/h.After firing, be 100 ℃/h cool to room temperature (20 ℃), then pulverize, screen, obtain using composition formula Li with cooling rate
1.0Mn
1.5Ni
0.5O
4.0The Li-mn-ni compound oxyde of expression.The BET specific area of these composite oxides is 0.40m
2/ g, the average grain diameter of being tried to achieve by laser method particle size distribution method is 10.7 μ m.
In addition, main modulation condition is as shown in table 1, and the various rerum naturas of resulting Li-mn-ni compound oxyde are as shown in table 2.
Table 1
| The compound that contains M | First ablating work procedure | Second ablating work procedure | ||||
| Kind | Addition (mole %) | Temperature (℃) | Time (h) | Temperature (℃) | Time (h) | |
| Embodiment 1 | MgO | 0.5 | 1000 | 12 | 600 | 15 |
| Embodiment 2 | MgO | 0.5 | 950 | 12 | 600 | 15 |
| Embodiment 3 | TiO 2 | 0.5 | 1000 | 12 | 600 | 15 |
| Comparative example 1 | - | - | 1000 | 12 | 600 | 15 |
Table 2
| BET specific area (m 2/g) | Average grain diameter (μ m) | Mn solution-off amount (ppm) | |
| Embodiment 1 | 0.38 | 10.6 | 86 |
| Embodiment 2 | 0.46 | 10.4 | 94 |
| Embodiment 3 | 0.37 | 10.9 | 75 |
| Embodiment 4 | 0.40 | 10.6 | 80 |
| Embodiment 5 | 0.38 | 10.3 | 83 |
| Embodiment 6 | 0.48 | 8.2 | 98 |
| Comparative example 1 | 0.40 | 10.7 | 103 |
[performance evaluation]
In order to following method measured resulting Li-mn-ni compound oxyde in embodiment and the comparative example manganese solution-off amount, and use the discharge capacity ratio of these composite oxides as energy sustainment rate, the highest average working voltage and the 4.5～5.0V/3.0～5.0V of the coulombic efficiency of the initial stage discharge capacity of the lithium secondary battery of positive active material, the 10th circulation, the 20th circulation.The result of manganese ion solution-off amount is as shown in table 2, and result in addition is as shown in table 3.
In addition, the initial stage discharge capacity curve in embodiment 1,2,3 and the comparative example 1 is represented as Fig. 1, Fig. 2, Fig. 3, Fig. 4 respectively.
＜manganese solution-off amount 〉
With the li-mn-ni compound oxide of 1g put into can be airtight Teflon (registered trade mark, special teflon) container in.This container is put into one evening of vacuum desiccator that is heated to 120 ℃, remove moisture.After container taken out, under the air ambient of drying, 5g electrolyte is put into Teflon (registered trade mark) container, the lid of covered container from vacuum drier.Electrolyte is that the volume ratio at 1 liter ethylene carbonate and diethyl carbonate is to have dissolved 1 mole LiPF in 1: 2 the mixed liquor
6Form.Shake container up and down, composite oxides and electrolyte are fully mixed after, container put into 80 ℃ thermostat and placed for 1 week.Therebetween, container of concussion in per 2 to 3 days mixes both.After a week, from thermostat, take out container, with the electrolyte in the filter filtering container of 0.1 μ m.The filtrate of 1g is put into the measuring bottle of 100ml, in this measuring bottle, add ultra-pure water: the mixed solvent of ethanol=80: 20 (weight ratio), dilution constant volume.After measuring bottle fully shaken, measure the concentration of Mn with the atomic absorption analysis standard measure.Based on this quantitative values, how many Mn dissolvings are arranged in the electrolyte of conversion 5g, calculate manganese solution-off amount.
＜initial stage discharge capacity 〉
Li-mn-ni compound oxide 5.7g, conductive agent (the Super P of conductive carbon, Erachem society system) 0.15g and adhesive (Kynoar) 0.15g are mixed.Then, add the N-methyl pyrrolidone of about 5ml, make uniform coating with mixer.On the thin slice of aluminum, drying is 2 hours under 120 ℃, has obtained positive wafer thin thus with applying coating.Applied thickness is 120 μ m.After suppressing positive wafer thin, be stamped into the size of 15mm, obtain positive plate.Use this positive plate, re-use each member such as barrier film, negative pole, collector plate, installation accessory, outside terminal, electrolyte, made lithium secondary battery.Use metallic lithium foil as negative pole, using volume ratio at 1 liter ethylene carbonate and diethyl carbonate is the LiPF of 1 mole of dissolving in 1: 2 the mixed liquor
6Solution as electrolyte.For this lithium secondary battery, the initial stage discharge capacity when having measured 25 ℃.Charging is that current value is 0.5C and reaches 5.0V in the mode of CCCV (finishing to the charging of the current value of 0.05C), discharge be current value be 0.2C and in the mode of CC to 3.0V.
The coulombic efficiency of＜the 10 circulation 〉
For the lithium secondary battery of use in the above-mentioned initial stage discharge capacity mensuration, measure the discharge capacity of the 10th circulation and the charging capacity of the 10th circulation, charging capacity * 100 of being circulated by discharge capacity/10th of the 10th circulation calculate the 10th coulombic efficiency that circulates.
The discharge capacity sustainment rate of＜the 20 circulation 〉
For the lithium secondary battery of use in the above-mentioned initial stage discharge capacity mensuration, measure the discharge capacity of the 1st circulation and the charging capacity of the 20th circulation, calculate the 20th discharge capacity sustainment rate that circulates by discharge capacity * 100 of circulating in discharge capacity/1st of the 20th circulation.
The energy sustainment rate of＜the 20 circulation 〉
For the lithium secondary battery that uses in the above-mentioned initial stage discharge capacity mensuration, obtain the energy density (discharge capacity * voltage) of the 1st circulation and the energy density of the 20th circulation, calculate the energy sustainment rate of the 20th circulation by energy density/energy density * 100 of the 1st circulation of the 20th circulation.
＜the highest average working voltage 〉
For the lithium secondary battery that uses in the above-mentioned initial stage discharge capacity mensuration, the cyclical voltage the when operating voltage in the time of will discharging in the circulation of being measured is the highest is as the highest average working voltage.
The discharge capacity ratio of＜4.5-5.0V/3.0-5.0V 〉
For the lithium secondary battery that uses in the above-mentioned initial stage discharge capacity mensuration, in order to determine the ratio in 5V discharge capacity zone/(5V discharge capacity zone+4V discharge capacity zone), termination (Cut) voltage in when discharge is made as 4.5V and 3.0V, calculates the discharge capacity ratio by discharge capacity * 100 of discharge capacity/3.0～5.0V of 4.5～5.0V.
Table 3
| Initial stage discharge capacity (mAh/g) | The coulombic efficiency (%) of the 10th circulation | The capacity sustainment rate (%) of the 20th circulation | The energy sustainment rate (%) of the 20th circulation | The highest average working voltage (V) | 4.5-5.0V/ the discharge capacity of 3.0-5.0V is than (%) | |
| Embodiment 1 | 140.2 | 99.1 | 95.7 | 95.1 | 4.64 | 92.2 |
| Embodiment 2 | 139.9 | 98.3 | 96.6 | 96.1 | 4.65 | 94.0 |
| Embodiment 3 | 140.3 | 99.0 | 95.5 | 95.1 | 4.64 | 92.9 |
| Embodiment 4 | 138.8 | 98.5 | 95.6 | 95.4 | 4.65 | 92.0 |
| Embodiment 5 | 140.5 | 99.2 | 95.2 | 94.9 | 4.63 | 92.6 |
| Embodiment 6 | 138.5 | 98.0 | 93.5 | 92.6 | 4.64 | 91.9 |
| Comparative example 1 | 139.0 | 97.7 | 92.7 | 91.7 | 4.64 | 91.4 |
Can clearly know by the result shown in the table 3, the Li-mn-ni compound oxyde that obtains among the use embodiment 1～6 is as the lithium secondary battery of positive active material, compare coulombic efficiency, capacity sustainment rate and energy sustainment rate height with the lithium secondary battery of comparative example 1.And, result and Fig. 1, Fig. 2, Fig. 3 and Fig. 4 by the discharge capacity ratio of table 3 can clearly know, the use Li-mn-ni compound oxyde that obtains among the embodiment 1,2,3 is as the lithium secondary battery of positive active material, compare with the lithium secondary battery of comparative example 1, near change in voltage 4V (smooth section of curve) is little, and the ratio that exists in 5V zone becomes big.
Claims (7)
1. manufacture method with the Li-mn-ni compound oxyde of following general formula (1) expression,
Li
xMn
1.5-yNi
0.5-zM
y+zO
4-w (1)
In the formula, 0.9＜x＜1.1, y＞0, z＞0,0＜y+z＜0.1,0≤w＜2, M represents to be selected from least a metallic element in magnesium, aluminium, titanium and the zirconium,
It is characterized in that: the mixture that will contain lithium, manganese, nickel and M is fired under 950～1050 ℃ of temperature, after cooling obtains precursor, fires this precursor again under 550～650 ℃ of temperature.
2. the manufacture method of Li-mn-ni compound oxyde as claimed in claim 1 is characterized in that: the described mixture that contains lithium, manganese, nickel and M is made of the complex chemical compound of lithium compound, manganese and nickel and the compound that contains M.
3. the manufacture method of Li-mn-ni compound oxyde as claimed in claim 1, it is characterized in that: the BET specific area of described precursor is 0.2～0.6m
2/ g.
4. the manufacture method of Li-mn-ni compound oxyde as claimed in claim 3, it is characterized in that: the average grain diameter of described precursor is 5～15 μ m.
5. the manufacture method of Li-mn-ni compound oxyde as claimed in claim 1, it is characterized in that: described M is magnesium or titanium.
6. Li-mn-ni compound oxyde is characterized in that: it is made by the described method of claim 1.
7. a lithium secondary battery is characterized in that: possess the positive pole that contains the described Li-mn-ni compound oxyde of claim 6.
Applications Claiming Priority (2)
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|---|---|---|---|
| JP2004219098 | 2004-07-27 | ||
| JP2004219098A JP4411157B2 (en) | 2004-07-27 | 2004-07-27 | Lithium manganese nickel composite oxide, method for producing the same, and lithium secondary battery using the same |
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| CN100492722C CN100492722C (en) | 2009-05-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908620A (en) * | 2010-06-02 | 2010-12-08 | 东北大学 | Method for preparing lithium ion battery material LiNi0.5Mn1.5-xTixO4 |
| CN101651203B (en) * | 2009-09-22 | 2011-06-01 | 西安交通大学 | Solid-state synthesis method of preparing magnesium-doped lithium nickel manganese oxide anode material |
| CN104067433A (en) * | 2012-01-18 | 2014-09-24 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same |
| CN105680033A (en) * | 2016-04-13 | 2016-06-15 | 天津巴莫科技股份有限公司 | 5V spinel nickel lithium manganate material and preparation method thereof |
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| KR100790835B1 (en) | 2006-05-10 | 2008-01-03 | 주식회사 엘지화학 | Method of Preparing Material for Lithium Secondary Battery of High Performance |
| KR100794142B1 (en) | 2006-05-10 | 2008-01-16 | 주식회사 엘지화학 | Material for Lithium Secondary Battery of High Performance |
| JP5194835B2 (en) * | 2008-01-24 | 2013-05-08 | 株式会社豊田中央研究所 | Lithium manganese composite oxide, lithium ion secondary battery, and method for producing lithium manganese composite oxide |
| JP4968944B2 (en) * | 2008-02-01 | 2012-07-04 | 日本化学工業株式会社 | Composite carbonate and method for producing the same |
| JP2013129589A (en) * | 2011-11-22 | 2013-07-04 | Tanaka Chemical Corp | Composite oxide, method for producing the same, positive electrode for lithium secondary battery, and lithium secondary battery |
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| JP2013191381A (en) * | 2012-03-13 | 2013-09-26 | Nissan Motor Co Ltd | Planar stacked battery and manufacturing method therefor |
| EP2837600B1 (en) | 2012-07-09 | 2017-11-29 | LG Chem, Ltd. | Precursor for preparing lithium composite transition metal oxide |
| WO2014010862A1 (en) | 2012-07-09 | 2014-01-16 | 주식회사 엘지화학 | Precursor for preparing lithium composite transition metal oxide, method for preparing same, and lithium composite transition metal oxide |
| DE102015115691B4 (en) | 2015-09-17 | 2020-10-01 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung | Lithium-nickel-manganese-based transition metal oxide particles, their production and their use as electrode material |
-
2004
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2005
- 2005-07-26 CN CNB2005100853575A patent/CN100492722C/en active Active
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101651203B (en) * | 2009-09-22 | 2011-06-01 | 西安交通大学 | Solid-state synthesis method of preparing magnesium-doped lithium nickel manganese oxide anode material |
| CN101908620A (en) * | 2010-06-02 | 2010-12-08 | 东北大学 | Method for preparing lithium ion battery material LiNi0.5Mn1.5-xTixO4 |
| CN104067433A (en) * | 2012-01-18 | 2014-09-24 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same |
| CN104067433B (en) * | 2012-01-18 | 2016-09-14 | 三菱化学株式会社 | Nonaqueous electrolytic solution and use the nonaqueous electrolyte battery of this nonaqueous electrolytic solution |
| CN105680033A (en) * | 2016-04-13 | 2016-06-15 | 天津巴莫科技股份有限公司 | 5V spinel nickel lithium manganate material and preparation method thereof |
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| JP2006040715A (en) | 2006-02-09 |
| KR20060046769A (en) | 2006-05-17 |
| CN100492722C (en) | 2009-05-27 |
| KR101216886B1 (en) | 2012-12-28 |
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