CN102598371A - Process for production of positive electrode material for lithium ion secondary battery - Google Patents

Process for production of positive electrode material for lithium ion secondary battery Download PDF

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CN102598371A
CN102598371A CN201080047968XA CN201080047968A CN102598371A CN 102598371 A CN102598371 A CN 102598371A CN 201080047968X A CN201080047968X A CN 201080047968XA CN 201080047968 A CN201080047968 A CN 201080047968A CN 102598371 A CN102598371 A CN 102598371A
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zirconium
positive electrode
lithium
manufacturing approach
aqueous
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巽功司
河里健
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AGC Seimi Chemical Ltd
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AGC Seimi Chemical Ltd
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract

Disclosed is a process for producing a lithium-containing oxide having excellent charge-discharge cycle durability, a low free alkali content, high discharge capacity, high filling properties and high volume capacity density. Specifically disclosed is a process for producing a positive electrode material for a lithium ion secondary battery, which is characterized by comprising: bringing a lithium-containing oxide represented by general formula LiaNibCocMndMeO2 (wherein M represents at least one element selected from the group consisting of transition metal elements excluding Ni, Co and Mn, aluminum, tin, zinc, and alkali earth metals; 0.95 <= a <= 1.2; 0 <= b <= 1; 0 <= c <= 1; 0 <= d <= 0.6 and 0 <= e <= 0.2, wherein a + b + c + d + e = 2) into contact with an aqueous zirconium solution having a zirconium concentration of 5 to 1000 ppm; and separating the aqueous zirconium solution from the lithium-containing oxide, thereby producing the positive electrode material.

Description

The manufacturing approach of lithium ion secondary battery anode material
Technical field
The present invention relates to the lithium ion secondary battery anode material manufacturing approach, use the positive pole and the lithium rechargeable battery of the positive electrode that obtains by this manufacturing approach.
Background technology
In recent years, along with the portability of equipment, wireless penetration development, for small-sized, light weight and have high-energy-density nonaqueous electrolytic solution secondary batteries such as lithium rechargeable battery require increasingly high.For the general positive electrode that nonaqueous electrolytic solution secondary battery is used, known have a LiCoO 2, LiNi 1/3Co 1/3Mn 1/3O 2, LiNi 0.6Co 0.2Mn 0.2O 2, LiNiO 2, LiNi 0.8Co 0.2O 2, LiMn 2O 4, LiMnO 2Composite oxides (in the present invention, abbreviating lithium composite xoide sometimes as) Deng lithium and transition metal etc.
Wherein, use LiCoO 2As the lithium secondary battery of carbon such as positive electrode, use lithium alloy, graphite or carbon fiber,, therefore be widely used as battery with high-energy-density owing to can obtain the high voltage of 4V level as negative pole.
In addition, LiNi 1/3Co 1/3Mn 1/3O 2, LiNi 0.6Co 0.2Mn 0.2O 2, LiNiO 2, LiNi 0.8Co 0.2O 2Deng positive electrode,, therefore placed hopes on as material cheaply because the content of Co of high price is few.And known in these positive electrodes, the content of Ni is many more, and the charge/discharge capacity of per unit weight is many more, can make the high battery of energy density.
But; In all positive electrodes; The charge and discharge cycles durability that the minimizing of discharge capacity, fillibility, the volume capacity density relevant with the discharge capacity of per unit volume, the discharge capacity that causes with repeated charge is relevant, with charged state under during long-time the placement gas generated relevant preservation characteristics and all be inadequate when processing electrode to the free alkali number of the relevant coating connection of the coating state of collector body etc., can't be satisfied the positive electrode of above-mentioned each item fully.
In order to address these problems, various researchs had been carried out in the past.For example, after having proposed to be dispersed in lithium/nickel/cobalt composite oxide in the water, filter the positive electrode that obtains; Lithium/nickel/cobalt composite oxide is dispersed in the water, and then after adding phosphoric acid, filters the positive electrode that obtains; After cobalt acid lithium stirred in the aqueous solution of the acidity that contains sulfuric acid, nitric acid or hydrochloric acid, the positive electrode (with reference to patent documentation 1, patent documentation 2) that filtration obtains.
In addition; The particle that has also proposed to have the lithium composite xoides such as complex Li-Mn-oxide of spinel structure is dispersed in water or the alcohol; Add the alkoxide of aluminium or zirconium then, and then add entry, make alkoxide add water decomposition after; Filter the positive electrode (with reference to patent documentation 3, patent documentation 4) that heating obtains.
In addition, also proposed dissolving Zr (OC 3H 7) 4The 2-propanol solution in disperse lithium nickel manganese composite oxide, stir, filter, heat-treat the positive electrode (with reference to patent documentation 5) that obtains at 500 ℃ then.
In addition, the aqueous solution that has also proposed to have dissolved Zr mixes the positive electrode that is fired into (with reference to patent documentation 6) with the lithium cobalt composite oxide.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid is opened the 2000-090917 communique
Patent documentation 2: Japanese Patent Laid is opened the 2003-123755 communique
Patent documentation 3: Japanese Patent Laid is opened the 2001-313034 communique
Patent documentation 4: Japanese Patent Laid table 2003-500318 communique
Patent documentation 5: Japanese Patent Laid is opened the 2005-310744 communique
Patent documentation 6: International Publication WO2007/052712 communique
Summary of the invention
The problem that invention will solve
As stated, though carried out various researchs in the past, still can't be satisfied the lithium composite xoide of various characteristicses such as discharge capacity, fillibility, volume capacity density, charge and discharge cycles durability and free alkali number fully.
For example, in the positive electrode of in patent documentation 1 and patent documentation 2, putting down in writing, though through cleaning the particle surface of lithium composite xoide; Can remove the alkali cpd of particle surface, and the minimizing of visible free alkali number, but owing to particle surface contacts with water or the high acid of acid degree; Therefore the ion of lithium, nickel, cobalt or manganese can be from the particle surface stripping of positive electrode; It is unstable that crystal structure becomes, and show the extreme deterioration of charge and discharge cycles durability, is the positive electrode of not anti-practicality.
In addition; In the positive electrode of in patent documentation 3 and patent documentation 4, putting down in writing; The solvent that contacts with lithium composite xoide is organic solvents such as alcohol, and the difficult dissolving alkali cpd of organic solvent can't be removed the alkali cpd of the particle surface that is present in lithium composite xoide.Therefore, free alkali number is high, and under the situation that the positive electrode as battery uses, when being processed into electrode, the slurry of dispersion positive electrode becomes gel or positive electrode peels off from collector body, the deterioration of visible coating.In addition, preservation characteristics is also poor, and along with repeated charge, and produce gas and make cell expansion at inside battery, also be the positive electrode of not anti-practicality.
And then; About record in the patent documentation 5, in the organic solvent of the alkoxide that has dissolved zirconium, disperse lithium composite xoide and filter, positive electrode that heat treatment obtains; The solvent that lithium composite xoide is disperseed is an organic solvent, owing to can't remove the alkali cpd of the particle surface that is present in lithium composite xoide, therefore free alkali number is high; And preservation characteristics and coating are poor, also are the positive electrodes of not anti-practicality.
The positive electrode of record in the patent documentation 6; Show the raising of charge and discharge cycles durability, but the reduction of free alkali number seldom, free alkali number is high; Under situation about using as positive electrode; When being processed into electrode, the slurry that is dispersed with positive electrode becomes gel or positive electrode peels off from collector body, the deterioration of visible coating.In addition, preservation characteristics is also poor, and along with repeated charge, produce gas and make cell expansion at inside battery, also be the positive electrode of not anti-practicality.
In addition, the free usually high positive electrode of alkali number, when its slurry from be dispersed in solvent is processed into electrode, exist become easily gel, positive electrode from collector body peel off, the problem of coating difference.In addition; The positive electrode that free alkali number is high uses as the positive pole of battery, under charged state long preservation, or during prolonged and repeated discharging and recharging, the decomposition reaction of electrolyte takes place; And be accompanied by heating; Produce gas and water such as carbon dioxide, substantial connection to the expansion of battery, break, have the problem of preservation characteristics difference.
Therefore; The object of the present invention is to provide good, the free alkali number of charge and discharge cycles durability low and have a manufacturing approach of the positive electrode of high discharge capacity, high fillibility and high volume capacity density; Contain the positive pole of the positive electrode that obtains through this manufacturing approach, and the lithium rechargeable battery that contains this positive electrode.
The means of dealing with problems
The deep research back that the inventor continues is found; Through using following positive electrode; Can address the above problem: after contacting through the aqueous zirconium in the concentration range that makes lithium composite xoide and regulation, separating Li composite oxides from aqueous zirconium and the positive electrode that obtains.
The present invention is based on that above-mentioned new opinion obtains, with following content as purport.
(1) a kind of manufacturing approach of lithium ion secondary battery anode material is characterized in that: make general formula Li aNi bCo cMn dM eO 2(wherein, M representes to be selected from least a kind of element in transition metal, aluminium, tin, zinc and the alkaline-earth metal beyond Ni, Co and the Mn.0.95≤a≤1.2,0≤b≤1,0≤c≤1; 0≤d≤0.6,0≤e≤0.2, a+b+c+d+e=2) lithium composite xoide and the concentration of zirconium of expression are after the aqueous zirconium of 5～1000ppm contacts; From lithium composite xoide, separate aqueous zirconium, obtain positive electrode.
(2) according to the manufacturing approach of record in above-mentioned (1), wherein above-mentioned positive electrode is further heated under 50～1000 ℃ temperature.
(3) according to the manufacturing approach of record in above-mentioned (1) or (2), wherein above-mentioned aqueous zirconium is with the aqueous solution that is selected from zirconium carbonate ammonium, ammonium zirconium fluoride, zirconium chloride, zirconium nitrate, zirconium carbonate, zirconium oxycarbonate, potassium zirconium carbonate and obtains with at least a kind of compound dissolving in the water-soluble zirconates of organic acid chelating formation.
(4) according to the manufacturing approach of putting down in writing in each of above-mentioned (1)～(3), wherein the pH of above-mentioned aqueous zirconium is 3～12.
(5) according to the manufacturing approach of putting down in writing in each of above-mentioned (1)～(4), wherein making above-mentioned aqueous zirconium is that 1～20 times ratio contacts with it with the mass ratio with respect to lithium composite xoide.
(6) according to the manufacturing approach of putting down in writing in each of above-mentioned (1)～(5), the amount of the zirconium that contains in the wherein above-mentioned positive electrode is 10～800ppm.
(7) according to the manufacturing approach of putting down in writing in each of above-mentioned (1)～(6), the free alkali number that contains in the wherein above-mentioned positive electrode is below the 0.8mol%.
(8) according to the manufacturing approach of putting down in writing in each of above-mentioned (1)～(7), wherein represent in the above-mentioned general formula of above-mentioned lithium composite xoide 0.97≤a≤1.1,0.2≤b≤0.8,0.1≤c≤0.4,0.1≤d≤0.4,0≤e≤0.1.
(9) a kind of manufacturing approach of lithium ion secondary battery anode; It is characterized in that: positive electrode, conductive agent, adhesive and the solvent that will use the manufacturing approach put down in writing in each of above-mentioned (1)～(8) to obtain; After being coated on the slurry that obtains on the metal forming, obtain positive pole except that desolvating through heating.
(10) a kind of manufacturing approach of lithium rechargeable battery is characterized in that: state lamination sept and negative pole on the positive pole that the manufacturing approach of (9) obtains in the use, be accommodated in it in battery case after, inject electrolyte and obtain secondary cell.
(11) a kind of lithium ion secondary battery anode, this positive pole is the positive pole that contains positive electrode, conductive agent and adhesive, it is characterized in that: the positive electrode that this positive electrode is to use the method put down in writing in each of above-mentioned (1)～(8) to obtain.
(12) a kind of lithium rechargeable battery is characterized in that: comprise positive pole, negative pole and electrolyte, and the positive pole of record in these just very above-mentioned (11).
The invention effect
The present invention provides a kind of manufacturing approach that can obtain following positive electrode: this positive electrode is useful as the positive pole of lithium rechargeable battery; And the charge and discharge cycles durability is good; Free alkali number is low, has high discharge capacity, high fillibility and high volume capacity density.In addition, the present invention also provides positive electrode and lithium ion secondary battery anode with good battery performance and the lithium rechargeable battery that use is obtained by above-mentioned manufacturing approach.
In addition, in the present invention, through measuring the amount of alkali cpd on grain circle that free alkali number evaluation is present in particle surface or the particle of positive electrode.The free alkali number of the positive electrode that obtains through the present invention is low, can prevent the gelation of the slurry of positive electrode, improves coating, and can suppress the gas that the decomposition reaction of electrolyte follows and the generation of water, and prevents the expansion etc. of battery, can improve preservation characteristics.
About the positive electrode that obtains among the present invention, have above-mentioned good characteristic why, though its mechanism may not be clear and definite, infer as follows.
Generally speaking, lithium composite xoide is that the lithium source is mixed with the transition metal source that contains nickel, cobalt and manganese etc., and the raw mix that obtains is fired into.In this lithium composite xoide, there are the lithium atom or because the insufficient and residual alkali cpds such as lithium compound of reaction that depart from the lattice-site of lattice and exist.When having used the battery repeated charge of the positive electrode that constitutes by described alkali composite oxides; Since above-mentioned alkali cpd from particle surface or particle the grain circle's stripping to electrolyte; The composition of positive electrode changes; Perhaps promote the decomposition of electrolyte, therefore become the reason of degradation of cell performance such as coating or preservation characteristics.
But; In order to remove above-mentioned alkali cpd; When only water or acidic aqueous solution clean the grain circle of particle surface or particle of lithium composite xoide; Compositions such as lithium, nickel, cobalt, manganese become ion and from the particle surface stripping of lithium composite xoide, it is unstable that crystal structure can become, charge and discharge cycles durability deterioration.
On the other hand, according to the present invention, the particle through making lithium composite xoide contacts with aqueous zirconium in the concentration range of regulation, can remove alkali cpd effectively.In addition, owing to can suppress the stripping of lithium, nickel, cobalt, manganese etc., even the situation of stripping is arranged, in the position of the atom of stripping zirconium takes place also and replace, therefore being considered to the charge and discharge cycles durability can deterioration.And, when the amount of the alkali cpd in the lithium composite xoide reduces, owing to use the gelation of its slurry to be suppressed, so the coating raising, and the gas that in battery, produces minimizing, therefore be considered to preservation characteristics and improve.
So; Among the present invention; Through contacting, can obtain the effect of the composition stripping in good effect of removing the alkali cpd in the lithium composite xoide and the inhibition lithium composite xoide with the aqueous zirconium that with respect to lithium composite xoide is the concentration range of regulation; Improve simultaneously the charge and discharge cycles durability greatly, and significantly reduce free alkali number.
In addition; Compound through making zirconium contacts with lithium composite xoide with the state of the aqueous solution; The particle surface that can prevent lithium composite xoide adheres to excessive zirconium compounds; And the zirconium amount of the aqueous zirconium that the particle surface that can will derive from positive electrode contains is controlled in the suitable scope, thereby can under the prerequisite that does not reduce discharge capacity, improve the charge and discharge cycles durability.
Embodiment
As stated; The present invention is made up of following operation: the particle of the lithium composite xoide of forming with regulation is contacted with the aqueous zirconium of the concentration of regulation; After removing the alkali cpd that is present in particle surface; From lithium composite xoide, separate aqueous zirconium, obtain the positive electrode that lithium rechargeable battery is used.
The lithium composite xoide that uses among the present invention is used general formula Li aNi bCo cMn dM eO 2Expression.The definition of a in the general formula, b, c, d and e is distinguished as stated, wherein, and preferred 0.97≤a≤1.1,0.2≤b≤0.8; 0.1≤c≤0.4,0.1≤d≤0.4,0≤e≤0.1, more preferably 0.99≤a≤1.05; 0.4≤b≤0.7,0.15≤c≤0.3,0.15≤d≤0.3,0≤e≤0.05.In addition, when paying attention to speed characteristic, preferred 0.97≤a≤1.03, b=0,0.97≤c≤1, d=0,0≤e≤0.03.
In addition, consider preferred 1.05≤a≤1.2,0.1≤b≤0.3,0.05≤c≤0.20,0.45≤d≤0.60,0≤e≤0.03 from the aspect that obtains jumbo lithium rechargeable battery with low cost.In addition, the lithium composite xoide that uses among the present invention also can replace speed characteristic and the fail safe that improves battery through the part with its oxygen atom with fluorine atom.Under this situation, preferably 0.001～5 mole of % with oxygen atom replaces with fluorine atom, and more preferably 0.5～3 mole of % with oxygen atom replaces with fluorine atom.
The manufacturing approach of the lithium composite xoide that uses among the present invention can be used solid phase method, coprecipitation method etc., does not have special qualification.As nickel source, cobalt source, manganese source, M element source, specifically can use hydroxide, oxide, oxyhydroxide of each element etc.In addition, can also use each element combination in any of nickel, cobalt, manganese, M element and the heavy altogether heavy altogether hydroxide that obtains, heavy oxide, heavy oxyhydroxide etc. altogether altogether.In addition,, do not have special qualification, but be preferably selected from least a kind in lithium carbonate and the lithium hydroxide, wherein more preferably lithium carbonate as the lithium source.The average grain diameter in lithium source is preferably 2～25 μ m.In addition, sometimes as required can be in the mixture of the raw material that contains lithium source etc. mixing water.
Among the present invention; The value that the mole of the lithium in the lithium composite xoide obtains divided by the total amount of the mole of Ni, Co, Mn and M element, be that mol ratio a/ (b+c+d+e) is preferably 0.95～1.20; Further be preferably 0.97～1.10, be preferably 0.99～1.05 especially.In this case, can promote the growth of the particle of lithium composite xoide, obtain more highdensity particle.
In addition, from can considering with the aspect that low cost obtain jumbo lithium rechargeable battery, preferred 0.45≤d≤0.60, mol ratio a/ (b+c+d+e) is 1.05～1.20, further is preferably 1.10～1.20.As the preferred object lesson of described lithium composite xoide, can enumerate: Li 1.2Ni 0.175Co 0.10Mn 0.525O 2, Li 1.2Ni 0.175Co 0.05Mn 0.575O 2, Li 1.2Ni 0.175Co 0.10Mn 0.525O 1.98F 0.02, Li 1.17(Ni 1/6Co 1/6Mn 4/6) 0.83O 2Deng.
Among the present invention, the M element is at least a kind of element in transition metal, Al, Sn, Zn and the alkaline-earth metal that is selected from beyond Ni, Co and the Mn.The transition metal of 4 families, 5 families, 6 families, 7 families, 8 families, 9 families, 10 families or 11 families of above-mentioned transition metal indication cycle table.Wherein, the M element is preferably selected from least a kind among Al, Ti, Zr, Hf, Nb, Ta, Mg, Sn and the Zn.Consider from aspects such as discharge capacity, fail safe, charge and discharge cycles durability that particularly the M element more preferably is selected from least a kind among Al, Ti, Zr, Hf and the Mg, is preferably selected from least a kind among Al, Zr and the Mg especially.
Among the present invention, the average grain diameter of the particle of lithium composite xoide is preferably 8～25 μ m, more preferably 10～20 μ m.In addition, the specific area of lithium composite xoide can use the BET method to measure, and is preferably 0.1～1.5m 2/ g, more preferably 0.15～1.2m 2/ g is preferably 0.20～1.0m especially 2/ g.
Among the present invention, aqueous zirconium is meant the aqueous solution of the compound of dissolving zirconium.The aqueous zirconium that uses among the present invention does not comprise suspension-turbid liquid and colloid form, be dissolved at least the zirconium source as solid constituent through the visual degree that can't discern.Scope below the zirconium concentration of the aqueous solution is preferred.Be limited to 1000ppm on the zirconium concentration, be preferably 500ppm, more preferably 200ppm.In addition, the following 5ppm that is limited to of zirconium concentration is preferably 20ppm, more preferably 50ppm.Zirconium concentration is in this scope the time, and the free alkali number that contains in the positive electrode that obtains is low, and shows the tendency that the charge and discharge cycles durability improves, and is preferred.On the other hand, when the concentration of aqueous zirconium was higher than 1000ppm, because excessive zirconium is attached on the lithium composite xoide, discharge capacity reduced, and is not preferred therefore.In addition, when zirconium concentration was lower than 5ppm, owing to form the element stripping of the particle of lithium composite xoide, therefore charge and discharge cycles durability deterioration was not preferred.In addition, among the present invention, the concentration ppm of zirconium is a quality criteria.
The pH of aqueous zirconium is preferably 3～12, is preferably 5～11 especially.In addition, the pH of the aqueous zirconium after separating from lithium composite xoide is preferably 7～13, is preferably 9～12 especially.About the pH of aqueous zirconium, when being lower than above-mentioned scope, lithium composite xoide is exposed in the acid environment, and strippings from particle such as Li, Ni, Co and Mn have the tendency of charge and discharge cycles durability deterioration.In addition, when pH is higher than above-mentioned scope, can't fully remove the alkali cpd on the particle surface that is present in lithium composite xoide or grain circle, have the high tendency of free alkali number.
For the zirconium source that forms aqueous zirconium, can use water miscible zirconium compounds, wherein, preferred inorganic acid and/or organic acid and zirconium or the compound that contains zirconium react the zirconates that obtains.As this zirconates, more preferably be selected from zirconium carbonate ammonium, ammonium zirconium fluoride, zirconium chloride, zirconium nitrate, zirconium carbonate, zirconium oxycarbonate, potassium zirconium carbonate and the water-soluble zirconates that forms with the organic acid chelating at least a kind.The water-soluble zirconates that forms with the organic acid chelating is to make organic acid and zirconium reactions such as saturated fatty acid, alkyd or unsaturated dicarboxylic, is formed by zirconium atom and organic acid chelating.In addition, as this organic acid, be preferably selected from least a kind organic acid in formic acid, acetate, propionic acid, citric acid, glycolic, hydroxyl butyric acid, malic acid, tartaric acid, maleic acid, oxalic acid, malonic acid, butanedioic acid and the glyoxalic acid.Wherein, more preferably be selected from least a kind organic acid in citric acid, malic acid, tartaric acid, maleic acid, oxalic acid, malonic acid, butanedioic acid and the glyoxalic acid, special optimization citric acid, tartaric acid or glyoxalic acid.
In the above-mentioned zirconium source, be preferably selected from zirconium carbonate ammonium, ammonium zirconium fluoride and the water-soluble zirconates that forms with citric acid, glyoxalic acid or tartaric acid chelating at least a kind compound.And, more preferably be selected from zirconium carbonate ammonium, ammonium zirconium fluoride and the water-soluble zirconates that forms with citric acid or glyoxalic acid chelating at least a kind compound, further be preferably selected from least a kind compound in zirconium carbonate ammonium and the ammonium zirconium fluoride.As above-mentioned zirconium source, zirconium carbonate ammonium obtains and low price easily, and positive electrode therefrom is functional, therefore preferred especially.Dissolved the aqueous zirconium in said zirconium source through use, can remove alkali cpd from the particle surface of lithium composite xoide, the elements such as lithium, nickel, cobalt, manganese that suppress to form lithium composite xoide simultaneously are from the particle surface stripping, and the reduction of the alkali number of realizing dissociating.
In addition, when using the organic solvent dissolved the zirconium source to replace aqueous zirconium, can't remove the alkali cpd of the particle surface that is present in lithium composite xoide, cause electrolyte decomposition and make cell expansion, the preservation characteristics deterioration.In addition, use Zr (OC 3H 7) 4As the zirconium source, and when making water in the solvent, because zirconium alkoxide adds water decomposition, become suspension-turbid liquid or pulpous state, therefore the particulate of excessive zirconium compounds is attached to the particle surface of lithium composite xoide, can not reduce free alkali number, and then discharge capacity reduces.
The method that contacts with aqueous zirconium for the particle that makes lithium composite xoide does not have special qualification; For example; Can example: the aqueous zirconium placing beaker or stainless steel tank etc. adds lithium composite xoide; Use stirring means such as agitator to mix, perhaps in pump, carry out boiler water circulation the powder of aqueous zirconium and lithium composite xoide is carried out method of mixing.In addition, also can use the lithium composite xoide that is opposite on the filter cloth to carry out the aqueous zirconium spraying, and then carry out the method for suction strainer, perhaps filter with filter press from the filter cloth below.Through with above-mentioned method contact, can effectively remove the alkali cpd of the particle surface that is present in lithium composite xoide.In addition, do not have special qualification, but be preferably 10 seconds time of contact～8 hours, more preferably 1 minute～5 hours, be preferably 5 minutes especially～3 hours for the condition that lithium composite xoide is contacted with aqueous zirconium.In addition, the temperature during contact is preferably 5～80 ℃, more preferably 10～60 ℃, is preferably 20～40 ℃ especially.In addition, the pressure during contact is preferably 0.5～3 air pressure, is preferably atmospheric pressure especially.
In addition, the ratio of the aqueous zirconium that contacts with lithium composite xoide, preferably with respect to lithium composite xoide, mass ratio is 1～20 times a scope.The ratio of the aqueous zirconium that contacts with lithium composite xoide, wherein mass ratio is more preferably 3～10 times, is preferably 4～6 times especially.The ratio of this aqueous zirconium can make lithium composite xoide fully contact with aqueous zirconium in above-mentioned scope the time, can fully remove alkali cpd.When mixing ratio was higher than above-mentioned scope, the quantitative change of the aqueous zirconium of use was many, had the tendency that wastewater flow rate increases.
Among the present invention, with after aqueous zirconium contacts, carry out the separation of aqueous zirconium from lithium composite xoide at lithium composite xoide.The separation of described aqueous zirconium will be in order to carry out from the free alkali component separating that lithium composite xoide is dissolved into the aqueous zirconium from lithium composite xoide.As the method for from lithium composite xoide, separating aqueous zirconium, can take the whole bag of tricks.For example can enumerate: the method for press filtration, the method for centrifugation, method of pumping filtration etc.
Among the present invention,, can obtain positive electrode, but positive electrode preferably then carries out heat treated through from lithium composite xoide, separating aqueous zirconium.Heating-up temperature is preferably more than 50 ℃, more preferably more than 60 ℃, further is preferably more than 400 ℃, is preferably especially more than 600 ℃.In addition, heating-up temperature is preferably below 1000 ℃, more preferably below 900 ℃, is preferably especially below 830 ℃.When the lower limit of heating-up temperature is lower than said temperature, can not removes remaining water in the positive electrode that separates behind the aqueous zirconium fully, thereby cause battery performance to reduce.On the other hand, when the upper limit of heating-up temperature was higher than above-mentioned scope, the particles sintering of positive electrode also formed thick particle, and the guiding discharge capacity reduces sometimes, and perhaps speed characteristic reduces.The method of heating does not have special qualification, preferably uses roller kilns (Roller Hearth Kiln) or rotary kiln (Rotary kiln), under oxygen containing atmosphere, carries out.There is not special qualification heating time, preferred 1～24 hour, more preferably 2～18 hours, preferred especially 3～12 hours.
The positive electrode that obtains according to the present invention has low free alkali number, and this free alkali number is preferably below the 0.8mol% with respect to the lithium composite xoide that contains in the positive electrode, more preferably below the 0.7mol%.In addition; Consider from the time of contact that shortens lithium composite xoide and aqueous zirconium, the aspect that can effectively synthesize positive electrode of the present invention; The lower limit of free alkali number is preferably 0.01mol%, if the free alkali number of this degree, then to almost not influence of battery performance.When free alkali number is above-mentioned scope, when making electrode, when the slurry of positive electrode is coated collector body etc., have the tendency that slurry can gelation, can be easily and coating equably, improve coating.In addition, in the time of can also suppressing battery charge and long preservation or the generation of the gas during repeated charge-discharge cycles, and can prevent the expansion of battery to improve preservation characteristics.
Free alkali number among the present invention is the relevant value of amount of alkali cpd with the grain circle of particle surface that is present in positive electrode and particle.Should measure through following method by free alkali number: in the powder 1g of positive electrode, mix 50g water and stirred 30 minutes; It is 4.0 to pH that alkali in the filtrating that filtration is obtained, the liquid that merges with the cleaning fluid that uses 3 cleaning and filtering things of 10g moisture to obtain uses the watery hydrochloric acid titration, and the hydrochloric acid content that from titration, uses is obtained the free alkali number of positive electrode.
Residual a spot of zirconium in the positive electrode that obtains through the present invention, the amount of the residual zirconium that derives from aqueous zirconium is preferably 10～800ppm in the positive electrode, and more preferably 20～600ppm is preferably 50～300ppm especially.The amount of the zirconium that contains in the positive electrode owing to can obtain the positive electrode that the charge and discharge cycles durability is good and free alkali number is few in favorable reproducibility ground, is preferred therefore in above-mentioned scope the time.In addition, among the present invention, the amount of the zirconium that derives from aqueous zirconium that contains in this positive electrode is meant the residual amount of zirconium (the residual amount of Zr) sometimes.The residual amount of this zirconium can use ICP (inductively coupled plasma) luminescence analysis to measure.In addition, when containing zirconium in advance in the lithium composite xoide before contacting with aqueous zirconium, the residual amount of zirconium (the residual amount of Zr) is for deducting the value that obtains with the zirconium amount that contains in advance before aqueous zirconium contacts in the zirconium amount that from the positive electrode that uses icp analysis to measure, contains.
The percent consolidation that adds of the positive electrode that obtains through the present invention is preferably 2.7～3.6g/cm 3, 2.8～3.4g/cm more preferably 3In addition, the percent consolidation that adds among the present invention is meant that the powder 5g with positive electrode uses 0.32t/cm 2Exert pressure the time the apparent percent consolidation that adds.In addition, the average grain diameter of the particle of positive electrode is preferably 8～25 μ m, more preferably 10～20 μ m.In addition, the specific area of positive electrode uses the BET method to measure, and is preferably 0.1～1.5m 2/ g, more preferably 0.15～1.2m 2/ g is preferably 0.20～1.0m especially 2/ g.Among the present invention, average grain diameter is meant the value of the accumulation 50% of the volume particle size distribution that use laser light scattering particle size distribution device (for example, using day system Microtrack HRAX-100 of a machine dress company (day machine is adorned society) etc.) obtains.Among the present invention, sometimes this average grain diameter is called average grain diameter D50 or abbreviates D50 as.In addition, after the D10 that states be meant the value of accumulation 10%, D90 is meant the value of accumulation 90%.In addition, when the particle of positive electrode is made up of offspring, the average grain diameter of expression offspring, when the particle of positive electrode is primary particle, the average grain diameter of expression primary particle.In addition, the shape affects of the shape of particle of the positive electrode lithium composite xoide that receives to use in the raw material.
When the positive electrode that is obtained by the present invention is made anodal that lithium rechargeable battery uses, form through in the powder of positive electrode, mixing carbon class electric conducting material such as acetylene black, graphite, Ketjen black and jointing material.In the above-mentioned jointing material, preferably use Kynoar, polytetrafluoroethylene, polyamide, carboxymethyl cellulose, acrylic resin etc.Use solvent or decentralized medium are processed slurry or mixing thing with powder, electric conducting material and the jointing material of the positive electrode that the present invention obtains.It is made the positive pole that lithium rechargeable battery is used through the coating equivalent-load on positive electrode collectors such as aluminium foil, stainless steel foil.
In the lithium rechargeable battery of the positive electrode that uses the present invention to obtain,, can use porous matter polyethylene, the polyacrylic film of porous matter etc. as sept.In addition, the solvent as the electrolyte solution of battery can use all kinds of solvents, wherein is preferably carbonic ester.Carbonic ester can use any one in ring-type, the chain.As cyclic carbonate, can enumerate propylene carbonate, ethylene carbonate (EC) etc.As linear carbonate, can the example dimethyl carbonate, diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methylpropyl carbonate, carbonic acid isopropyl methyl ester etc.
Among the present invention, above-mentioned carbonic ester can use separately or use mixing more than 2 kinds.In addition, also can use with other solvent.In addition, different according to the material of negative electrode active material, when linear carbonate and cyclic carbonate are share, can improve flash-over characteristic, cyclic durability, efficiency for charge-discharge sometimes.
In addition; In the lithium rechargeable battery of the positive electrode that uses the present invention to obtain; Trade name Kynar) or the gel polymer electrolyte of vinylidene-perfluoro propyl vinyl ether copolymer also can in electrolyte, use and contain vinylidene fluoride-hexafluoropropylene copolymer (for example, Atochem (FR) Cedex 22, 94091 Paris La Defense, France (ア ト ケ system society) system:.As the solute that adds in above-mentioned electrolyte solvent or the polymer dielectric, preferably use with ClO 4 -, CF 3SO 3 -, BF 4 -, PF 6 -, AsF 6 -, SbF 6 -, CF 3CO 2 -, (CF 3SO 2) 2N -Deng as more than in the anionic lithium salts any.The concentration of the lithium salts that contains in electrolyte solvent or the polymer dielectric is preferably 0.2～2.0mol/l (liter), is preferably 0.5～1.5mol/l especially.When this concentration range, ionic conductance is big, and electrolytical conductivity increases.
In the lithium rechargeable battery of the positive electrode that uses the present invention to obtain, negative electrode active material can use the ability occlusion, discharge the material of lithium ion.The material that forms this negative electrode active material does not have special qualification, for example can enumerate: lithium metal, lithium alloy, material with carbon element, the oxide that is the main body with the metal of periodic table 14 or 15 families, carbon compound, carborundum compound, silicon oxide compounds, titanium sulfide, boron carbide compound etc.As material with carbon element, can use thermal decomposition organic substance under various thermal decomposition conditions and material or Delanium, native graphite, amorphous graphite, expanded graphite, flaky graphite etc.In addition, as oxide, can use with the compound of tin oxide as main body.As negative electrode collector, can use Copper Foil, nickel foil etc.Described negative pole, preferably through following method manufacturing: above-mentioned active material and organic solvent are carried out the mixing slurry of processing, this slurry are coated on the metal forming collector body, carry out drying, the compacting and obtain.
Shape for the lithium battery of the positive electrode that uses the present invention to obtain has no particular limits, and can select sheet, membranaceous, rugosity, convoluted round-ended cylinder shape, button-type etc. arranged according to purposes.
Embodiment
Below, through embodiment and comparative example the present invention is described particularly, but the present invention is not limited by these embodiment.Following example 1～example 5, example 11～example 13 and example 15～example 21 are embodiment, and routine 6～example 10 is a comparative example with example 14.
[example 1]
To make the atomic ratio of nickel, cobalt, manganese be Ni: Co: Mn=6 having dissolved nickelous sulfate, cobaltous sulfate and manganese sulfate: in 2: 2 the aqueous solution; Add continuously ammonium sulfate solution and sodium hydrate aqueous solution and make that the pH of the aqueous solution is 11.0, temperature is 50 ℃ while stirring, separate out common hypostasis.To overflow the amount of liquid in the mode conditioned reaction system, the heavy altogether slurries filtration that will overflow, washing then 80 ℃ of dryings, obtains the powder of nickel cobalt manganese composite hydroxide thus.The specific area of the powder of this complex hydroxide is 5.6m 2/ g, average grain diameter D50 are 11.8 μ m.
In the powder of the complex hydroxide that obtains, mix the powder of lithium hydroxide, in air atmosphere, burnt till 10 hours at 500 ℃.The thing that burns till that obtains is mixed once more, burnt till 24 hours,, obtain having Li through pulverizing at 900 ℃ 1.02(Ni 0.6Co 0.2Mn 0.2) 0.98O 2The powder of lithium composite xoide of composition.The specific area of the powder of this lithium composite xoide is 0.29m 2/ g, average grain diameter D50 are 14.0 μ m.After this powder being used the powder x-ray diffraction spectroscopic assay of CuK α line, can know similar structures for rhombohedral system (R-3m).Use the system RINT of company of science (リ ガ Network society) 2100 types in the mensuration.In addition,, confirm after using sweep electron microscope (below, be called SEM) to observe particle, be the offspring of a plurality of primary particles aggregate above-mentioned powder.In addition, use ICP to measure the zirconium amount that contains in the above-mentioned powder, the result is not for detecting.
Then, in zirconium content is the zirconium carbonate ammonium aqueous solution (Japanese light metal company (Japanese light metal society) the system ベ イ コ one ト 20) 0.71g of 14.1 quality %, add entry and process 1000g, obtaining zirconium concentration is the aqueous zirconium of 100ppm.In addition, the chemical formula of the zirconium carbonate ammonium of use is (NH 4) 2[Zr (CO 3) 2(OH) 2].The liquid agitation 10 minutes that will in this aqueous zirconium 1000g, add the pulpous state that the powder 200g of above-mentioned lithium composite xoide obtains.Then, use 5C number filter paper to carry out suction filtration and separating liquid the liquid that obtains and obtain shot-like particle.In addition, stir with the operation that separates and at room temperature carry out.The pH of aqueous zirconium is 9.0, and the pH of the aqueous zirconium after the separation is 11.8.This shot-like particle 120 ℃ of heating 5 hours, was heated 5 hours at 800 ℃ then.The shot-like particle that obtains is sieved, obtain the powder of positive electrode.The operation of stirring, separate, heating is all carried out under air atmosphere.The average grain diameter D50 of positive electrode is 15.3 μ m, and D10 is 8.1 μ m, and D90 is 33.6 μ m, and specific area is 0.25m 2/ g.
The powder 1g of above-mentioned positive electrode is mixed and stirs filtrating that the slurries filtration that obtained in 30 minutes obtains, cleans the washing lotion that obtains with filtrate for 3 times with 10g moisture and merge with water 50g, the aqueous hydrochloric acid solution titration of amalgamation liquid use 0.02mol/L to pH be 4.0.The free alkali number that the hydrochloric acid content that from titration, uses is obtained positive electrode is 0.56mol%.
The percent consolidation that adds of the particle of the positive electrode that obtains is 2.73g/cm 3, the zirconium amount that contains in the particle is 120ppm.Derive from the zirconium of aqueous zirconium amount, to be the residual amount of zirconium (the residual amount of Zr) be 120ppm.
Mass ratio with 90/5/5 mixes powder, acetylene black and the Kynoar powder of above-mentioned positive electrode, and adds the N-methyl pyrrolidone, makes slurry, uses the aluminium foil single face coating sizing-agent of scraper plate method (doctor blade method) to thick 20 μ m.The aluminium flake that drying obtains, 3 roll-ins are rolling makes the positive polar body sheet that lithium battery is used through carrying out.
Then, use aforesaid positive polar body sheet as positive pole, the metallic lithium foil of using thick 500 μ m is as negative pole, and negative electrode collector uses the nickel foil of 20 μ m, and sept uses the porous matter polypropylene of thick 25 μ m, and the LiPF of electrolyte working concentration 1M 6/ EC+DEC (1: 1) solution (is meant with LiPF 6Mixed solution for the volume ratio (1: 1) of the EC and the DEC of solute), in the argon gas glove box, be assembled into the simple and easy enclosed cell type of stainless steel lithium battery.
To this airtight simple and easy cell type lithium battery at 25 ℃ of electric currents, upper voltage limit 4.3V, (fixed current with 170mA charged, and cell voltage reaches that the fixed voltage with upper voltage limit charges behind the upper voltage limit with CCCV pattern charging 3 hours with every 1g positive active material 170mA.The charging interval that amounts to is 3 hours) after, be discharged to 2.75V with the current value of every 1g positive active material 85mA, obtain the initial stage discharge capacity.In addition,, charge repeatedly under the same conditions and discharge, carry out 30 charge and discharge cycles tests this battery.Consequently, 25 ℃, the initial stage discharge capacity of the positive active material of 2.75～4.3V are 167.4mAh/g, and the presented higher holdup after 30 charge and discharge cycles is 94.5%.
[example 2]
Except use zirconium concentration as the aqueous zirconium of 500ppm as the aqueous zirconium, other and example 1 operation equally, synthetic positive electrode, and measure each characteristic.The pH of aqueous zirconium is 9.1, and the pH of the aqueous zirconium after the separation is 10.8.Consequently, the average grain diameter D50 of the positive electrode that obtains is 14.6 μ m, and D10 is 7.8 μ m, and D90 is 26.1 μ m, and specific area is 0.28m 2/ g, adding percent consolidation is 2.83g/cm 3In addition, the free alkali number of the positive electrode that obtains is 0.39mol%, and the residual amount of zirconium is 320ppm.The initial stage discharge capacity is 166.8mAh/g, and the presented higher holdup after 30 charge and discharge cycles is 94.2%.
[example 3]
Except use zirconium concentration as the aqueous zirconium of 1000ppm as the aqueous zirconium, other and example 1 operation equally, synthetic positive electrode, and measure each characteristic.The pH of aqueous zirconium is 9.1, and the pH of the aqueous zirconium after the separation is 10.1.Consequently, the average grain diameter D50 of the positive electrode that obtains is 14.5 μ m, and D10 is 7.8 μ m, and D90 is 26.3 μ m, and specific area is 0.28m 2/ g, adding percent consolidation is 2.81g/cm 3The free alkali number of this positive electrode is 0.47mol%, and the residual amount of zirconium is 670ppm.The initial stage discharge capacity is 164.2mAh/g, and the presented higher holdup is 95.4%.
[example 4]
Except use zirconium concentration as the aqueous zirconium of 20ppm as the aqueous zirconium, other and example 1 operation equally, synthetic positive electrode, and measure each characteristic.The pH of aqueous zirconium is 8.9, and the pH of the aqueous zirconium after the separation is 11.9.Consequently, the average grain diameter D50 of the positive electrode that obtains is 15.4 μ m, and D10 is 8.0 μ m, and D90 is 31.3 μ m, and specific area is 0.29m 2/ g, adding percent consolidation is 2.75g/cm 3The free alkali number of this positive electrode is 0.58mol%, and the residual amount of zirconium is 22ppm.The initial stage discharge capacity is 169.6mAh/g, and the presented higher holdup is 94.2%.
[example 5]
Except use zirconium concentration as the aqueous zirconium of 5ppm as the aqueous zirconium, other and example 1 operation equally, synthetic positive electrode, and measure each characteristic.The pH of aqueous zirconium is 8.9, and the pH of the aqueous zirconium after the separation is 11.9.Consequently, the average grain diameter D50 of the positive electrode that obtains is 15.2 μ m, and D10 is 7.9 μ m, and D90 is 27.3 μ m, and specific area is 0.29m 2/ g, adding percent consolidation is 2.75g/cm 3The free alkali number of this positive electrode is 0.54mol%, and the residual amount of zirconium is 10ppm.The initial stage discharge capacity is 168.3mAh/g, and the presented higher holdup is 89.1%.
[example 6]
Except not with aqueous zirconium contact, other and example 1 operation equally synthesize positive electrode in example 1.That is, directly make the Li that has that obtains in the use-case 1 1.02(Ni 0.6Co 0.2Mn 0.2) 0.98O 2The lithium composite xoide of composition as positive electrode, measure each characteristic.The average grain diameter D50 of this positive electrode is 14.0 μ m, and D10 is 7.6 μ m, and D90 is 28.5 μ m, and specific area is 0.29m 2/ g, adding percent consolidation is 2.79g/cm 3The free alkali number of this positive electrode is 1.27mol%.After 1 same operation carried out the coating of electrode with example, coating was poor, and the phenomenon that positive electrode peels off from aluminium foil appears in the part of the electrode after coating, dry, roll-in are rolling.Use the electrode area of not peeling off to make battery, the initial stage discharge capacity is 167.7mAh/g, and the presented higher holdup is 94.7%.
[example 7]
Except using pure water to replace the aqueous zirconium, other are operated with example 1 equally, synthetic positive electrode, and measure each characteristic.The pH of water is 6.7, and the pH of the water after the separation is 12.1.Consequently, the average grain diameter D50 of the positive electrode that obtains is 16.1 μ m, and D10 is 8.4 μ m, and D90 is 29.9 μ m, and specific area is 0.22m 2/ g, adding percent consolidation is 2.72g/cm 3The free alkali number of this positive electrode is 0.54mol%, and the initial stage discharge capacity is 167.3mAh/g, and the presented higher holdup is 79.3%.
[example 8]
Except use zirconium concentration as the aqueous zirconium of 1ppm as the aqueous zirconium, other and example 1 operation equally, synthetic positive electrode, and measure each characteristic.The pH of aqueous zirconium is 8.8, and the pH of the aqueous zirconium after the separation is 11.9.Consequently, the average grain diameter D50 of the positive electrode that obtains is 14.6 μ m, and D10 is 8.0 μ m, and D90 is 26.0 μ m, and specific area is 0.26m 2/ g, adding percent consolidation is 2.86g/cm 3The free alkali number of this positive electrode is 0.53mol%, fails to confirm the zirconium amount that in particle, contains, the residual quantity not sufficient 10ppm of zirconium.The initial stage discharge capacity is 166.5mAh/g, and the presented higher holdup is 80.1%.
[example 9]
Except use zirconium concentration as the aqueous zirconium of 3000ppm as the aqueous zirconium, other and example 1 operation equally, synthetic positive electrode, and measure each characteristic.The pH of aqueous zirconium is 9.3, and the pH of the aqueous zirconium after the separation is 9.8.Consequently, the average grain diameter D50 of the positive electrode that obtains is 14.7 μ m, and D10 is 8.1 μ m, and D90 is 26.7 μ m, and specific area is 0.25m 2/ g, adding percent consolidation is 2.82g/cm 3The free alkali number of this positive electrode is 0.46mol%, and the residual amount of zirconium is 1600ppm.The initial stage discharge capacity is 162.4mAh/g, and the presented higher holdup is 93.4%.
[example 10]
In zirconium content is the zirconium carbonate ammonium aqueous solution (Japanese light metal corporate system) 1.33g of 14.1 quality %, add entry and process 30g, obtain aqueous zirconium.In addition, the chemical formula of the zirconium carbonate ammonium of use is (NH 4) 2[Zr (CO 3) 2(OH) 2].Then, with example 1 same synthetic have a Li 1.02(Ni 0.6Co 0.2Mn 0.2) 0.98O 2The powder (200g) of lithium composite xoide of composition in add this aqueous zirconium, mix, do not filter, while mix 80 ℃ of heating, drying obtains mixture.And then, this mixture 400 ℃ of heating 5 hours, is obtained the powder of positive electrode.The average grain diameter D50 of this positive electrode is 13.6 μ m, and D10 is 6.9 μ m, and D90 is 25.3 μ m, and specific area is 0.54m 2/ g, adding percent consolidation is 2.73g/cm 3The free alkali number of this positive electrode is 1.01mol%, and the residual amount of zirconium is 940ppm.After 1 same operation carried out the coating of electrode with example, coating was poor, and the phenomenon that positive electrode peels off from aluminium foil appears in the part of the electrode after coating, dry, roll-in are rolling.Use the electrode area of not peeling off to make battery, the initial stage discharge capacity is 168.0mAh/g, and the presented higher holdup is 94.0%.
[example 11]
To make the atomic ratio of cobalt, aluminium, magnesium, zirconium be Co: Al: Mg: Zr=0.969 having dissolved cobaltous sulfate, aluminum sulfate, magnesium sulfate and zirconium sulfate: in 0.015: 0.015: 0.001 the aqueous solution; Add continuously ammonium sulfate solution and sodium hydrate aqueous solution and make that pH is 11.0, temperature is 50 ℃ while stirring, separate out common hypostasis.To overflow the amount of liquid in the mode conditioned reaction system, filter the heavy altogether slurry that overflows, washing through 80 ℃ of dryings, obtains the powder of cobalt magnalium zirconium complex hydroxide then.The specific area of the powder of this complex hydroxide is 5.0m 2/ g, average grain diameter D50 are 12.7 μ m, and the zirconium amount that contains in the powder is 930ppm.
The quantitative lithium carbonate of hybrid regulatory in the complex hydroxide that so obtains, in air atmosphere, 1000 ℃ burn till 15 hours after, through pulverizing, obtain having Li 1.02(Co 0.969Al 0.015Mg 0.015Zr 0.001) 0.98O 2The powder of lithium composite xoide of composition.About the particle of this lithium composite xoide, observe with SEM, be the approaching spherical or elliptoid particle that constitutes by primary particle.The specific area of the powder of lithium composite xoide is 0.22m 2/ g, average grain diameter D50 are 12.2 μ m.Except using this lithium composite xoide, with example 1 likewise with after aqueous zirconium contact, filter, the separation aqueous zirconium obtains the powder of positive electrode from lithium composite xoide.The pH of aqueous zirconium is 9.0, and the pH of the aqueous zirconium after the separation is 10.8.
The average grain diameter D50 of the positive electrode that obtains is 12.5 μ m, and D10 is 7.1 μ m, and D90 is 22.3 μ m, and specific area is 0.17m 2/ g, adding percent consolidation is 3.06g/cm 3The free alkali number of this positive electrode is 0.04mol%, and the zirconium amount that contains in the particle is 1070ppm,, derives from the amount of the zirconium of aqueous zirconium that is, and promptly the residual amount of zirconium (the residual amount of Zr) is 140ppm.The initial stage discharge capacity is 146.0mAh/g, and the presented higher holdup is 86.0%.
[example 12]
To make the atomic ratio of nickel, cobalt, manganese be Ni: Co: Mn=3 having dissolved nickelous sulfate, cobaltous sulfate and manganese sulfate: in 3: 3 the aqueous solution; Add continuously ammonium sulfate solution and sodium hydrate aqueous solution and make that the pH of the aqueous solution is 11.0, temperature is 50 ℃ while stirring, separate out common hypostasis.To overflow the amount of liquid in the mode conditioned reaction system, filter the heavy altogether slurry that overflows, washing through 80 ℃ of dryings, obtains the powder of nickel cobalt manganese composite hydroxide then.The specific area of the powder of this complex hydroxide is 11.0m 2/ g, average grain diameter D50 are 10.8 μ m, do not detect the zirconium that contains in the powder.
The quantitative lithium carbonate powder of hybrid regulatory in the powder of the complex hydroxide that so obtains, in air atmosphere, 1000 ℃ burn till 15 hours after, through pulverizing, obtain having Li 1.02(Ni 0.333Co 0.333Mn 0.333) 0.98O 2The powder of lithium composite xoide of composition.About the particle of this lithium composite xoide, observe with SEM, be the offspring that a plurality of primary particles aggregate form, the shape of offspring is near spherical or ellipticity.The specific area of the powder of lithium composite xoide is 0.35m 2/ g, average grain diameter D50 are 11.0 μ m.Except using this lithium composite xoide, with example 1 likewise with after aqueous zirconium contact, filtration separates aqueous zirconium from lithium composite xoide, obtain the powder of positive electrode.The pH of aqueous zirconium is 9.0, and the pH of the aqueous zirconium after the separation is 11.2.
The average grain diameter D50 of the positive electrode that obtains is 11.5 μ m, and D10 is 5.6 μ m, and D90 is 23.3 μ m, and specific area is 0.39m 2/ g, adding percent consolidation is 2.58g/cm 3The free alkali number of this positive electrode is 0.14mol%, and the residual amount of zirconium is 130ppm.The initial stage discharge capacity is 147.2mAh/g, and the presented higher holdup is 96.9%.
[example 13]
Except the zirconium source is adopted ammonium zirconium fluoride, zirconium concentration be the aqueous zirconium of 100ppm as the aqueous zirconium, other and example 1 operation equally, the powder of synthetic positive electrode.In addition, the chemical formula of the ammonium zirconium fluoride of use is (NH 4) 2[ZrF 6].In addition, the pH of aqueous zirconium is 3.3, and the pH of the aqueous zirconium after the separation is 11.5.The average grain diameter D50 of positive electrode is 14.4 μ m, and D10 is 7.7 μ m, and D90 is 26.5 μ m, and specific area is 0.31m 2/ g, adding percent consolidation is 2.78g/cm 3The free alkali number of this positive electrode is 0.53mol%, and the residual amount of zirconium is 150ppm.The initial stage discharge capacity is 167.0mAh/g, and the presented higher holdup is 93.0%.
[example 14]
Except Zr (OC has been dissolved in use 3H 7) 4Make concentration be 0.01 quality % aqueous isopropanol, be that the aqueous isopropanol of zirconium concentration 8ppm replaces aqueous zirconium, and heating-up temperature is 500 ℃, heat beyond 1 hour, other and example 1 operation equally synthesize the powder of positive electrode.The average grain diameter D50 of positive electrode is 13.6 μ m, and D10 is 7.0 μ m, and D90 is 26.0 μ m, and specific area is 0.29m 2/ g, adding percent consolidation is 2.85g/cm 3The free alkali number of this positive electrode is 1.31mol%.After 1 same operation carried out the coating of electrode with example, coating was poor, and the phenomenon that positive electrode peels off from aluminium foil appears in the part of the electrode after coating, dry, roll-in are rolling.Use the electrode area of not peeling off to make battery, the initial stage discharge capacity is 167.3mAh/g, and the presented higher holdup is 87.8%.
[example 15]～[example 21]
In these embodiments, the heating-up temperature in the heating process after lithium composite xoide is separated from aqueous zirconium becomes the temperature of record in the table 1, operates equally with example 1, synthetic positive electrode.In addition, be shown in the table 1 with the example 1 same combined statement as a result of measuring each characteristic.
[table 1]
Figure BPA00001545848800201
Utilizability on the industry
The present invention provides a kind of manufacturing approach that can obtain following lithium composite xoide: this lithium composite xoide is useful as the positive pole of lithium rechargeable battery; And the charge and discharge cycles durability is good; Free alkali number is low, has high discharge capacity, high fillibility and high volume capacity density.In addition, the present invention also provides lithium ion secondary battery anode and the lithium rechargeable battery lithium composite xoide, that have good battery performance that a kind of use is obtained by above-mentioned manufacturing approach.
In addition, quote of the announcement of the full content of Japanese patent application 2009-249372 number specification, claims and the summary of filing an application on October 29th, 2009 here as specification of the present invention.

Claims (12)

1. the manufacturing approach of a lithium ion secondary battery anode material is characterized in that, makes general formula Li aNi bCo cMn dM eO 2Lithium composite xoide and the concentration of zirconium of expression is after the aqueous zirconium of 5～1000ppm contacts, from lithium composite xoide, to separate aqueous zirconium, obtains positive electrode,
In the said general formula, M representes to be selected from least a kind of element in transition metal, aluminium, tin, zinc and the alkaline-earth metal beyond Ni, Co and the Mn, 0.95≤a≤1.2,0≤b≤1,0≤c≤1,0≤d≤0.6,0≤e≤0.2, a+b+c+d+e=2.
2. manufacturing approach according to claim 1 is characterized in that, said positive electrode is further heated under 50～1000 ℃ temperature.
3. manufacturing approach according to claim 1 and 2; It is characterized in that said aqueous zirconium is with the aqueous solution that is selected from zirconium carbonate ammonium, ammonium zirconium fluoride, zirconium chloride, zirconium nitrate, zirconium carbonate, zirconium oxycarbonate, potassium zirconium carbonate and obtains with at least a kind of compound dissolving in the water-soluble zirconates of organic acid chelating formation.
4. according to each described manufacturing approach of claim 1～3, it is characterized in that the pH of said aqueous zirconium is 3～12.
5. according to each described manufacturing approach of claim 1～4, it is characterized in that making said aqueous zirconium is that 1～20 times ratio contacts with it with the mass ratio with respect to lithium composite xoide.
6. according to each described manufacturing approach of claim 1～5, it is characterized in that the amount of the zirconium that contains in the said positive electrode is 10～800ppm.
7. according to each described manufacturing approach of claim 1～6, it is characterized in that the free alkali number that contains in the said positive electrode is below the 0.8mol%.
8. according to each described manufacturing approach of claim 1～7, it is characterized in that, represent in the said general formula of said lithium composite xoide 0.97≤a≤1.1,0.2≤b≤0.8,0.1≤c≤0.4,0.1≤d≤0.4,0≤e≤0.1.
9. the manufacturing approach of a lithium ion secondary battery anode; It is characterized in that; With positive electrode, conductive agent, adhesive and the solvent that each described manufacturing approach of using claim 1～8 obtains, be coated on the slurry that obtains on the metal forming after, remove through heating and to desolvate.
10. the manufacturing approach of a lithium rechargeable battery is characterized in that, lamination sept and negative pole on the positive pole that uses the described manufacturing approach of claim 9 to obtain are accommodated in injection electrolyte in back in the battery case with it.
11. a lithium ion secondary battery anode, this positive pole is the positive pole that contains positive electrode, conductive agent and adhesive, it is characterized in that the positive electrode that this positive electrode is to use each described method of claim 1～10 to obtain.
12. a lithium rechargeable battery is characterized in that, comprises positive pole, negative pole and electrolyte, and this described positive pole of claim 11 just very.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105453313A (en) * 2013-08-22 2016-03-30 株式会社Lg化学 Cathode active material, lithium secondary battery comprising same, and method for preparing same
CN113646929A (en) * 2019-04-11 2021-11-12 杰富意矿物股份有限公司 Precursor, method for producing precursor, positive electrode material, method for producing positive electrode material, and lithium ion secondary battery
US20220085378A1 (en) * 2019-06-28 2022-03-17 Contemporary Amperex Technology Co., Limited Ternary positive electrode material with low gas generation and high capacity

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* Cited by examiner, † Cited by third party
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KR20130033154A (en) * 2011-09-26 2013-04-03 전자부품연구원 Positive active material, preparation method thereof and lithium secondary battery comprising the same
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US20200365874A1 (en) * 2017-11-22 2020-11-19 A123 Systems Llc Method and systems for metal doping on battery cathode materials
GB2569391A (en) * 2017-12-18 2019-06-19 Dyson Technology Ltd Compound
GB2569390A (en) 2017-12-18 2019-06-19 Dyson Technology Ltd Compound
GB2569392B (en) 2017-12-18 2022-01-26 Dyson Technology Ltd Use of aluminium in a cathode material
GB2569387B (en) 2017-12-18 2022-02-02 Dyson Technology Ltd Electrode
GB2569388B (en) * 2017-12-18 2022-02-02 Dyson Technology Ltd Compound
JP6994990B2 (en) * 2018-03-13 2022-01-14 住友化学株式会社 Lithium metal composite oxide powder, positive electrode active material for lithium secondary batteries, positive electrodes and lithium secondary batteries
WO2019193874A1 (en) * 2018-04-06 2019-10-10 パナソニックＩｐマネジメント株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6045771A (en) * 1995-11-24 2000-04-04 Fuji Chemical Industry Co., Ltd. Lithium-nickel complex oxide, a process for preparing the same and a positive electrode active material for a secondary battery
US20040265693A1 (en) * 2003-06-26 2004-12-30 Toyota Jidosha Kabushiki Kaisha Positive electrode active material and use thereof
CN101111457A (en) * 2005-09-27 2008-01-23 Agc清美化学股份有限公司 Process for producing lithium-containing composite oxide for positive electrode for lithium secondary battery

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19922522A1 (en) * 1999-05-15 2000-11-16 Merck Patent Gmbh Lithium based composite oxide particles for battery cathode, which are coated with one or more metal oxides
JP2004175609A (en) * 2002-11-26 2004-06-24 Ind Technol Res Inst Lithium cobaltate used for positive electrode of lithium ion battery, its manufacturing process and lithium ion battery
JP2005346956A (en) * 2004-05-31 2005-12-15 Hitachi Metals Ltd Positive electrode active material for nonaqueous lithium secondary battery, manufacturing method thereof, and nonaqueous lithium secondary battery using the positive electrode active material
KR101260539B1 (en) * 2006-03-02 2013-05-06 에이지씨 세이미 케미칼 가부시키가이샤 Positive electrode active material for rechargeable battery with nonaqueous electrolyte and method for manufacturing the same
JP5463652B2 (en) * 2008-11-14 2014-04-09 Ｔｄｋ株式会社 Active material and electrode manufacturing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6045771A (en) * 1995-11-24 2000-04-04 Fuji Chemical Industry Co., Ltd. Lithium-nickel complex oxide, a process for preparing the same and a positive electrode active material for a secondary battery
US20040265693A1 (en) * 2003-06-26 2004-12-30 Toyota Jidosha Kabushiki Kaisha Positive electrode active material and use thereof
CN101111457A (en) * 2005-09-27 2008-01-23 Agc清美化学股份有限公司 Process for producing lithium-containing composite oxide for positive electrode for lithium secondary battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105453313A (en) * 2013-08-22 2016-03-30 株式会社Lg化学 Cathode active material, lithium secondary battery comprising same, and method for preparing same
US9905841B2 (en) 2013-08-22 2018-02-27 Lg Chem, Ltd. Cathode active material and lithium secondary battery including the same, and method of manufacturing cathode active material
CN105453313B (en) * 2013-08-22 2019-03-26 株式会社Lg 化学 Positive electrode active materials and the lithium secondary battery comprising it and the method for preparing positive electrode active materials
CN113646929A (en) * 2019-04-11 2021-11-12 杰富意矿物股份有限公司 Precursor, method for producing precursor, positive electrode material, method for producing positive electrode material, and lithium ion secondary battery
US20220085378A1 (en) * 2019-06-28 2022-03-17 Contemporary Amperex Technology Co., Limited Ternary positive electrode material with low gas generation and high capacity
US11569510B2 (en) * 2019-06-28 2023-01-31 Contemporary Amperex Technology Co., Limited Ternary positive electrode material with low gas generation and high capacity

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