CN101510603A - Method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery - Google Patents
Method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery Download PDFInfo
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Abstract
The invention relates to a preparation method of Ni-Co lithium manganate which is a cathode material for a lithium ion battery, which pertains to the field of new energy material and preparative technique. The preparation method comprises the following steps: 1. a sulfate mixture solution of nickel, cobalt and manganese is prepared in accordance with a certain concentration; 2. the mixture solution, NH3 water and a sodium hydroxide solution are continuously injected into a reactor and stirred, and a spherical or quasi-spherical multiple hydroxide A of Ni, Co and Mn is obtained after the filtration, washing and drying are conducted over the mixture; 3. the dry multiple hydroxide A of Ni, Co and Mn is presintered to obtain a spherical multiple oxide B of Ni, Co and Mn; and 4. after being added with a right quantity of alcohol, the product B is evenly mixed with lithium hydroxide and the mixture is sintered, smashed and screened to obtain a spherical LizNixCoyMnxO2 cathode material C for the lithium ion battery. With the preparation method, the particle size and distribution of the product A and product B are easy to control and the spherical Ni-Co lithium manganate C with stable quality, high density, high capacity and high discharge plateau is obtained; therefore, the preparation method is applicable to stabilizing industrial production.
Description
Technical field:
The invention belongs to new energy materials and preparing technical field, the positive electrode that particularly a kind of lithium ion battery is used.
Background technology
Combination properties such as in recent years, along with the fast development of small portable electricity consumption equipment such as digital camera, notebook computer, mobile phone, that the battery that the market strong request drives these equipment has is small-sized, light weight and high power capacity.Lithium rechargeable battery has high discharge voltage and high energy density, has therefore captured the leading position of small-sized secondary batteries, and its market development free air anomaly is huge.
The positive battery material is the important component part in the lithium ion battery, and it has determined the many key performances of lithium ion battery.The main material of research has LiCoO at present
2, LiNiO
2, LiMnO
2, LiFePO
4Etc. multiple, LiCoO wherein
2Be the material that the comparative maturity combination property is best, use amount is maximum, but because the Co scarcity of resources, cost an arm and a leg and fail safe relatively poor, so people wish can be with more cheap material substitution Co.Though have the LiMnO of spinel structure
2Have advantages such as cost is low, safe and cheap, but its capacity is low and the low inherent defect that waits of discharge platform, has limited the use in the battery of high voltage, high power capacity.LiFePO
4Have advantage safe and with low cost, but its intrinsic density is low, the shortcoming of the low poor performance at low temperatures of discharge voltage has also limited it and used in the battery that high voltage, high-energy-density are arranged.LiNiO
2Cost is low, capacity is high but its structural instability is synthetic difficult, and fail safe and life-span are difficult to reach requirement, therefore also fails to drop into and commercially produces.
People wished once that Ni abundant relatively with resource, that price is lower or Mn substituted the part cobalt, the mode that forms cobalt nickel or nickel manganese solid solution is made lithium nickel cobalt dioxide or nickel LiMn2O4, after United States Patent (USP) has been described oxide dry mixed with the oxide of nickel and manganese for No. 5264201, pulverize through sintering and to obtain Li at last
xNi
2-x-yMn
yO
2The method of active material shown in (in the formula: 0.8≤x≤0.1, y≤0.2).United States Patent (USP) has been described for No. 5269110 with the oxide of manganese and β-(OH)
2Form LiNi through dry mixed
1-xMn
xO
2(0＜x≤0.2, y≤0.2), shown material synthetic method, the spy opens flat 10-69910 communique and has described with the synthetic Li of the method for co-precipitation
Y-x1Ni
1-x2-yM
xO
2(in the formula: M is selected from Al, Co, Mg, Fe or Mn element, 0＜x2≤0.5,0≤x2＜0.2, x=x1+x2,0.9≤y≤1.3,0＜x≤0.2, y≤0.2) is in the described prior art of above United States Patent (USP) or Japan Patent, in order to improve LiNiO
2Chemical property, keeping LiNiO
2Feature the time, all adopted interpolation Mn element.But because LiNiO
2And LiMnO
2Be separated from each other, be that final products are difficult to obtain single-phase complex chemical compound.During the coprecipitation method that uses, also can be owing to Mn
2+Be easy to be oxidized to Mn
3+Or Mn
4+And be difficult to obtain the compound that homogenizes.Therefore these materials have high-tension LiCoO substituting
2The time a lot of problems can appear.
To LiNiO
2Lithium nickel oxide substitute Ni with Part of Co and form LiNi
1-xCo
xO
2Also be to reduce cost at present to substitute LiCoO
2The research focus, the spy opens flat 2000-058053 and has announced a kind of preparation LiNi
1-xCo
xO
2Method, this method adopts a certain proportion of nickel salt, cobalt salt and lithium hydroxide to be blended in 300-700 ℃ of down no carbon dioxide roasting 2 hours, obtains through grinding after 700-900 ℃ of following roasting tied again.Though LiNi
1-xCo
xO
2People entertain great hope to it, but synthetic, the harsh difficulty of sintering condition, shortcomings such as poor stability also do not solve, and are still waiting further perfect.
Compound nickle cobalt lithium manganate (the LiNi of a new generation's ternary
xCo
yMn
zO
2) anode material for lithium-ion batteries is the focus of present people research, is to be hopeful to substitute LiCoO most
2Material.With LiCoO
2Compare and have the plurality of advantages that cost is low, reversible capacity is high, fail safe is good.Particularly nickle cobalt lithium manganate and LiCoO
2The high discharge platform that the 4V voltage level is all arranged is fit to do the battery use of high voltage, high power capacity.Chinese patent CN1622371A has announced a kind of method of making spherical high density manganese cobalt acid lithium, and this method is nickel salt, cobalt salt and manganese salt and NaOH, ammoniacal liquor to be reacted obtain Ni in the aqueous solution
1/3Co
1/3Mn
1/3(OH)
2Presoma is blended in 750-950 ℃ of sintering with lithium carbonate then and obtains the nickel manganese cobalt acid lithium of grain through 3-7 μ m.China publication CN101229928A has announced a kind of preparation method of spherical nickel-cobalt lithium manganate material, it has adopted with carbonate is that precipitation reagent obtains nickel manganese cobalt mixed carbonate presoma, then gained presoma and lithium salts are blended in 480-550 ℃ of presintering 4-6 hour after again 850-950 ℃ of insulation after 15-25 hour natural cooling obtain.Chinese patent CN1101226998A has announced the preparation method of high-density lithium ion anode material nickel manganese cobalt acid lithium, has adopted in this method nickel compound, cobalt compound, manganese compound mixing granulation, obtains intermediate product (Ni
1/3Co
1/3Mn
1/3) O
2Then with a certain proportion of lithium compound mixed sintering, at the final LiNi that arrives through broken classification
1/3Co
1/3Mn
1/3O
2Product.In existing these technology of having announced, the employing co-deposition method can be than the easier nickel cobalt manganese that makes of the method for dry powder blend sintering in other even doping of molecular level, help finally obtaining evenly single-phase nickel manganese cobalt acid lithium, but since codeposition when synthetic Co particularly Mn oxidation takes place easily, manganese is extremely easily by Mn
2+Change into Mn
3+Or Mn
4+Nickel cobalt and manganese are produced separates, grow up owing to the variation of doped chemical valence state also can influence spheroid in addition, and then be difficult to obtain bigger density.The presoma that adopts carbonate deposition with the process of lithium salts sintering in, the CO that decomposes in the time of also can be because of sintering
2The charge balance that influences in the material distributes.
The present inventor gives one's full attention to the density of further raising nickle cobalt lithium manganate and the importance of discharge voltage, thereby obtain highdensity spherical solid solution after the objective of the invention is to make nickel, cobalt, manganese evenly to disperse by atomic level, and by rational allocation nickel cobalt manganese solid solution in ratio and appropriate sintering process found to manifest and had high power capacity, the nickle cobalt lithium manganate positive active material method of high voltage capability feature.
Summary of the invention:
At the deficiencies in the prior art and defective, technical problem to be solved by this invention provides a kind of manufacture method of making high density, high power capacity and high-tension nonaqueous electrolyte nickle cobalt lithium manganate positive electrode active materials.
The present invention specifically takes following three steps to realize; Concrete technical method and the effect that reaches below are described respectively.
At first, 1), x:y:x promptly that the ratio of 2x+y=1 is mixed with the mixed solution that tenor is 40-100g/L with nickel salt, cobalt salt, manganese salt in molar ratio, 0.1≤x≤0.4,0.2≤y≤0.8 wherein, and satisfy 2x+y=1; 2), preparation contains the sodium hydroxide solution of 2mol-6mol/L and the ammonia spirit of 2-15mol/L; 3), will stir in the nickel cobalt-manganese salt mixed solution that prepare, sodium hydroxide solution, the continuous injecting reactor of ammonia spirit respectively, regulate the flow and the ratio of ammoniacal liquor flow of nickel cobalt-manganese salt mixed solution, control NH
3/ (Ni+Co+Mn) mol ratio is regulated the flow of sodium hydroxide solution simultaneously between 0.4-1.5, and the pH value in the control reactor remains between 8-11, and reactant liquor is discharged continuously from overfall; 4) add nitrogen, sulphite, nitrite, hydrazine water in the synthetic reaction with step 3), antioxidant is to prevent the oxidation in this course of reaction of manganese, cobalt; 5), product that step 3) reaction is discharged separates in solid-liquid separator, after washing gained solids to washings with water and reaching below the PH8.5, solids at 100-150 ℃, is dried and is obtained nickel cobalt manganese mixed hydroxides A after 1-2 hours; 6), the resulting nickel cobalt of step 5) manganese mixed hydroxides A put into sintering furnace between 300-500 ℃, carry out pre-burning, obtain the mixed oxide dry powder B of nickel manganese cobalt through the cooling sub-sieve; 7), nickel cobalt manganese mixed oxides B that step 6) is obtained, 10%-20% ethanolic solution, deionized water and place blender to mix through the lithium salts that milled processed is crossed to obtain slurry, the control charge ratio is Li/ (Ni+Co+Mn) mol ratio 1.03-1.08; 8), the slurry of step 7) placed to burn separates stove, be warming up to 800-1000 ℃ of insulation after 6-24 hour, be cooled to 400--600 ℃ of insulation cold quenching after 2-6 hour with the speed of 10 ℃-20 ℃ of per minutes again; 9), the product that step 8) is obtained obtains the spherical nickel-cobalt LiMn2O4 through pulverizing, sub-sieve.
Described nickel salt is selected from nickelous sulfate, nickel chloride or nickel nitrate, and cobalt salt is selected from cobaltous sulfate, cobalt chloride, cobalt nitrate, and manganese salt is selected from manganese sulfate, manganese chloride, manganese nitrate; And during the preparation of mixed solution, the mol ratio of nickel and manganese remains the proportionate relationship of 1:1; After the mixed solution product is discharged reactor, adopt the liquid particles separation equipment, the particle diameter bigger particle separation of reaction in the resulting spherical nickel-cobalt manganese mixing hydrogen-oxygen thing come out to carry out subsequent treatment process, and particle diameter refills in the reactor than granule and grows up once more.And product nickel cobalt manganese mixed hydroxides A mixes with lithium salts by after forming cobalt-nickel-manganese oxide compound B 300-500 ℃ of pre-burnings again, sintering, and wherein sintering is divided into the following steps formation:
First section: the mixture of cobalt-nickel-manganese oxide compound and lithium salts, directly be heated to 800-1100 ℃ after, be incubated 6-24 hours;
Second section: after cooling to 400--600 ℃ with 10 ℃/min behind the high temperature sintering, be incubated 2-6 hours;
The 3rd section: second section products therefrom obtained the spherical nickel-cobalt LiMn2O4 through cold quenching, pulverizing, sub-sieve.
Comparing the present invention with technology in the past has the following advantages at synthesis step:
1, the proportionate relationship preparation (wherein y ≧ 1/3) of the nickel that the solution preparation must be pressed among the present invention, cobalt, manganese molal quantity=x:y:x.One of key character of the present invention is that in the final products nickle cobalt lithium manganate, nickel all is Ni
2+, cobalt all is Co
3+, manganese all is Mn
4+, can not sneak into other dephasigns.The relation that in synthetic blending process, keeps keeping eventually nickel and manganese 1:1, the neutral equilibrium that helps the metal compound valency in the nickle cobalt lithium manganate behind the sintering, form the R-3m stratiform hexagonal structure homogeneous structure structure of complete homogeneous, this structure produces useful variation to the performance of material, makes nickle cobalt lithium manganate have smooth, higher discharge voltage plateau.In particular for obtaining the nickle cobalt lithium manganate of high discharge voltage, keep under the prerequisite of such proportion scale relation, the content that suitably improves Co surpasses 1/3 or the effect of the higher discharge platform that also can be improved.Technology in the past is not clear and definite to the discharge voltage that can further improve material in the positive active material nickle cobalt lithium manganate when cobalt content content in the ratio of nickel, cobalt, manganese surpasses 1/3, not have clearly the relation that when the improving cobalt content ratio of the nickel in the material, manganese must strict maintenance 1:1 yet.
2, one of feature of the present invention is to add excessive reducing agent and inert protective gas to reaction system in building-up process; purpose is in order effectively to have prevented Co and the Mn oxidation in synthetic reaction process; help growing up of nickel hydroxide cobalt manganese spheroid, keep the purity of synthetic product nickel hydroxide cobalt manganic acid lithium.In the building-up process in the reaction solution oxygen of trace Co will be oxidized to trivalent by divalent moiety, Mn all is oxidized to trivalent by divalence or more than the trivalent.If oxidation reaction takes place in building-up process, will catalytic reactor in new one-tenth nuclear reaction, ball-shape nickel hydroxide cobalt manganese particle mean size synthetic in the reactor is reduced, if Mn by the micro amount of oxygen oxidation in the solution after, the Mn of formation
2O
3Also can cause the reduction of nickel hydroxide cobalt manganese purity, follow-up sintering be obtained complete R-3m structure produce serious harmful effect, not only can not get highdensity ball-shape nickel hydroxide cobalt manganese the chemical property of final product nickle cobalt lithium manganate is seriously descended.
3, one of feature of the present invention is the resulting product that after the sedimentation of application of weight settlement separator big particle diameter feed separation come out, the material Returning reactor continued growth of small particle diameter.The material that the density of the product that obtains is like this discharged than direct overflow has bigger raising, can obtain 100% highdensity nickel hydroxide manganese cobalt acid lithium, high density product yield height, good economical benefit.If the mode that adopts dry powder to separate can produce 10-30% small particle diameter byproduct.Existing in the past technology all in continuous building-up process reactor material directly overflow after wash, dry and obtain ball-shape nickel hydroxide cobalt manganese from the reaction overfall, the density of this material has the leeway of further raising.
The presintering of step 2, compound nickel hydroxide cobalt manganese
One of feature of the present invention is after obtaining compound nickel hydroxide cobalt manganic acid lithium, warm pre-burning in directly carrying out, the high density composite nickel hydroxide cobalt manganese that step 1 obtains is given birth to temperature to 300--500 ℃ of certain fixed value with 5 ℃/minute speed, be incubated 2-4 hours, form the composite oxides (Ni of nickel cobalt manganese
xCo
yMn
x)
3O
4, because the temperature of presintering is low, oxygen is difficult for damaged Ni in the sintering furnace in this presintering process
xCo
yMn
x(OH)
2In cobalt finish by divalence easily and be oxidized to trivalent, manganese is oxidized to the part transition process of trivalent by divalence, it is good to form the electric charge coupling, the homogeneous structure structure of even tissue.Because a grain growth of the low formation of sintering temperature secondary spherical particle is slower, help keeping less size simultaneously, also create conditions for reducing follow-up sintering temperature and shortening time.
Composite oxides (the Ni of step 3, nickel cobalt manganese
xCo
yMn
x)
3O
4Mix the back high temperature sintering with lithium compound
One of feature of the present invention is that the sintering of this step carries out in two steps:
1, first section sintering: cobalt-nickel-manganese oxide compound and lithium compound are carried out dry mixed, also can add an amount of ethanolic solution, the mixed of pressing Li/ (Ni+Co+Mn)=1.02-1.08 of the ratio of the total metal molar in the lithium compound in lithium and the nickel, cobalt and manganese oxide is even, the temperature sintering that is heated under the oxygen atmosphere between 800-1000 ℃ is being arranged, be incubated 6-24 hour.
2, second section sintering: temperature was reduced to 600-700 ℃ of insulation after 3-6 hour, directly enters cold quenching in the water.
3, second section sintering cold quenching product oven dry, grinding, pulverizing, sub-sieve had both obtained nonaqueous electrolyte nickel manganese lithium cobaltate cathode active material.
Compare double sintering method of the present invention with technology in the past following advantage arranged:
1, one of feature of the present invention is to have adopted sintering process in advance, at composite oxides with before lithium salts mixes, the state of oxidation of Co, Mn part is finished, this section sintering mainly decomposes based on lithium salts and the diffusion process of lithium, so just can reduce temperature at sintering, shorten under the condition of sintering time, still can obtain complete crystallization, lamellar tissue's evident characteristic phase structure.This architectural feature helps the raising cycle life of material and the stability of material.Because sintering temperature reduces and the shortening of sintering temperature, make once the g and D of footpath grain not really abundant simultaneously, helped improving the diffusion velocity of lithium ion in material, increase the discharge capacity of material, and discharge voltage.
2, because in the process of high temperature sintering, can cause the oxygen content deficiency in the material, make material lattice structure imperfect and then influence the performance of material.Oxygen in low temperature insulation a period of time supplementary material can remedy the structure deterioration that material causes because of the sample disappearance, if in low sintering process as oxygen blast gas then effect is more obvious.
Embodiment:
The invention will be further described below in conjunction with specific embodiment, but the present invention is not constituted any limitation.
The preparation method of anode material lithium nickle cobalt manganic acid of lithium ion battery of the present invention mainly comprises the steps to form:
1), x:y:x promptly that the ratio of 2x+y=1 is mixed with the mixed solution that tenor is 40-100g/L with nickel salt, cobalt salt, manganese salt in molar ratio, 0.1≤x≤0.4,0.2≤y≤0.8 wherein, and satisfy 2x+y=1;
2), preparation contains the sodium hydroxide solution of 2mol-6mol/L and the ammonia spirit of 2-15mol/L;
3), will stir in the nickel cobalt-manganese salt mixed solution that prepare, sodium hydroxide solution, the continuous injecting reactor of ammonia spirit respectively, regulate the flow and the ratio of ammoniacal liquor flow of nickel cobalt-manganese salt mixed solution, control NH
3/ (Ni+Co+Mn) mol ratio is regulated the flow of sodium hydroxide solution simultaneously between 0.4-1.5, and the pH value in the control reactor remains between 8-11, and reactant liquor is discharged continuously from overfall;
4) add nitrogen, sulphite, nitrite, hydrazine water in the synthetic reaction with step 3), antioxidant is to prevent the oxidation in this course of reaction of manganese, cobalt;
5), product that step 3) reaction is discharged separates in solid-liquid separator, after washing gained solids to washings with water and reaching below the PH8.5, solids at 100-150 ℃, is dried and is obtained nickel cobalt manganese mixed hydroxides A after 1-2 hours;
6), the resulting nickel cobalt of step 5) manganese mixed hydroxides A put into sintering furnace between 300-500 ℃, carry out pre-burning, obtain the mixed oxide dry powder B of nickel manganese cobalt through the cooling sub-sieve;
7), nickel cobalt manganese mixed oxides B that step 6) is obtained, 10%-20% ethanolic solution, deionized water and place blender to mix through the lithium salts that milled processed is crossed to obtain slurry, the control charge ratio is Li/ (Ni+Co+Mn) mol ratio 1.03-1.08;
8), the slurry of step 7) placed to burn separates stove, be warming up to 800-1000 ℃ of insulation after 6-24 hour, be cooled to 400--600 ℃ of insulation cold quenching after 2-6 hour with the speed of 10 ℃-20 ℃ of per minutes again;
9), the product that step 8) is obtained obtains the spherical nickel-cobalt LiMn2O4 through pulverizing, sub-sieve.Wherein said nickel salt is selected from nickelous sulfate, nickel chloride or nickel nitrate, and cobalt salt is selected from cobaltous sulfate, cobalt chloride, cobalt nitrate, and manganese salt is selected from manganese sulfate, manganese chloride, manganese nitrate.In addition, when the preparation of mixed solution, the mol ratio of nickel and manganese remains the proportionate relationship of 1:1.After the mixed solution product is discharged reactor, adopt the liquid particles separation equipment, the particle diameter bigger particle separation of reaction in the resulting spherical nickel-cobalt manganese mixing hydrogen-oxygen thing come out to carry out subsequent treatment process, and particle diameter refills in the reactor than granule and grows up once more.Product nickel cobalt manganese mixed hydroxides A mixes with lithium salts by after forming cobalt-nickel-manganese oxide compound B 300-500 ℃ of pre-burnings again, sintering.
Wherein, sintering is divided into the following steps formation:
First section: the mixture of cobalt-nickel-manganese oxide compound and lithium salts, directly be heated to 800-1100 ℃ after, be incubated 6-24 hours;
Second section: after cooling to 400--600 ℃ with 10 ℃/min behind the high temperature sintering, be incubated 2-6 hours;
The 3rd section: second section products therefrom obtained the spherical nickel-cobalt LiMn2O4 through cold quenching, pulverizing, sub-sieve.
Embodiment 1:a, solution preparation: with nickelous sulfate (NiSO
47H
2O), cobaltous sulfate (CoSO
46H
2O), manganese sulfate (MnSO
4H
2O) mixed solution of preparation Ni+Co+Mn total mole number 1.2mol/L makes Ni:Co:Mn=1:1:1 in the solution (mol ratio); The sodium hydroxide solution of preparation 6mol/L; The NH of preparation 8mol/L
3The aqueous solution.
B, add an amount of hydrazine water every 30 fens clockwise reactors, in reactor, feed nitrogen simultaneously from reaction beginning.With the measuring pump solution that implantation step a prepares in having the kickback device respectively, fixedly the injection rate of the injection rate of nickel cobalt manganese solution and ammoniacal liquor keeps NH
3/ (Ni+Co+Mn)=0.8.The injection rate of regulating sodium hydroxide solution makes the pH value in the reactor remain on 10.5.Temperature in the reactor is controlled at 55 ℃ ± 1 ℃.Open the measuring pump of reactor bottom, the mixed material in gravitational settler in the injecting reactor, partial material is from from settler Returning reactor suitable for reading.The mixed material that collection distributes from the settler infraoral washs to PH8 with pure water, press filtration, and material is through 100 ℃, and oven dry in 2 hours gets ball-shape nickel hydroxide nickel cobalt manganese, apparent density 1.68g/cm
3, tap density 2.35g/cm
3
C, the ball-shape nickel hydroxide cobalt manganese that step b is obtained are sent in the sintering furnace, are warming up to 400 ℃ with the speed of 5 ℃/min and keep 5 hours.Get spherical nickel-cobalt manganese composite oxide, apparent density 1.74g/cm through sub-sieve
3, tap density 2.42g/cm
3
D, the spherical compound nickel, cobalt and manganese oxide that step c is obtained mix with lithium hydroxide, mixed proportion is Li/ (Ni+Co+Mn)=1.05, send into sintering furnace and be warming up to 950 ℃ of maintenances after 18 hours with 10 ℃/min speed, with being cooled to 600 ℃ and keeping after 5 hours cold quenching of 20 ℃/min to room temperature, nickle cobalt lithium manganate.
E, with the steps d product pulverize, sub-sieve, the spherical nickle cobalt lithium manganate of finished product.The granularity that records this product is 5-25 μ m, tap density 2.76g/cm
3With material with carbon element as cooperating negative pole to make battery, under the room temperature that records first discharge capacity be 162mAh/g, the above capacity of 1C discharge 3.6V accounts for total capacity 68%.
Embodiment 2: the ratio preparation in Ni:Co:Mn=0.3:0.4:0.3 when preparing except that nickel cobalt manganese mixed solution, other process conditions are the same with embodiment 1.Get the apparent density 1.67g/cm of nickel hydroxide cobalt manganese
3, tap density 2.38g/cm
3The spherical nickel-cobalt manganese composite oxide, apparent density 1.73g/cm
3, tap density 2.39g/cm
3Must product spherical nickel-cobalt LiMn2O4 after tested granularity be that 5-28 μ m is normal distribution, tap density 2.75g/cm
3。With material with carbon element as cooperating negative pole to make battery, under the room temperature that records first discharge capacity be 165mAh/g, the above capacity of 0.2C discharge 3.6V accounts for total capacity 72%.
Embodiment 3:, the ratio preparation in Ni:Co:Mn=0.25:0.5:0.25 when preparing except that nickel cobalt manganese mixed solution, other process conditions are the same with embodiment 1.Get the apparent density 1.70g/cm of nickel hydroxide cobalt manganese
3, tap density 2.36g/cm
3The spherical nickel-cobalt manganese composite oxide, apparent density 1.72g/cm
3, tap density 2.38g/cm
3The spherical nickel-cobalt LiMn2O4 that obtains granularity after tested is that 5-27 μ m is normal distribution, tap density 2.78g/cm
3。With material with carbon element as cooperating negative pole to make battery, survey under the room temperature first discharge capacity be 168mAh/g, 0.2C discharge 3.6V capacity accounts for total capacity 76%.
Comparative example 1: do not add reducing agent as different from Example 1 in the building-up process and also do not add inert gas shielding, other process conditions are identical with embodiment 1.Get the apparent density 1.36g/cm of nickel hydroxide cobalt manganese
3, tap density 2.14g/cm
3The spherical nickel-cobalt manganese composite oxide, apparent density 1.44g/cm
3, tap density 2.18g/cm
3The spherical nickel-cobalt LiMn2O4 that obtains granularity after tested is that 3-18 μ m is normal distribution, tap density 2.42g/cm
3。With material with carbon element as cooperating negative pole to make battery, survey under the room temperature first discharge capacity be 145mAh/g, 0.2C discharge 3.6V capacity accounts for total capacity 37%.
Comparative example 2: in the building-up process, material is directly directly discharged from the overfall of reactor as different from Example 1, and other process conditions are identical with fact Example.Get the apparent density 1.55g/cm of nickel hydroxide cobalt manganese
3, tap density 2.26g/cm
3The spherical nickel-cobalt manganese composite oxide, apparent density 1.57g/cm
3, tap density 2.28g/cm
3The spherical nickel-cobalt LiMn2O4 that obtains granularity after tested is that 4-20 μ m is normal distribution, tap density 2.53g/cm
3。With material with carbon element as cooperating negative pole to make battery, survey under the room temperature first discharge capacity be 155mAh/g, 0.2C discharge 3.6V capacity accounts for total capacity 55%.
Comparative example 3: with more different be not add reducing agent in the building-up process, the material after the synthetic reaction directly overflows from reactor.Other conditions are identical with embodiment 1.Get the apparent density 1.28g/cm of nickel hydroxide cobalt manganese
3, tap density 2.10g/cm
3The spherical nickel-cobalt manganese composite oxide, apparent density 1.36g/cm
3, tap density 2.12g/cm
3The spherical nickel-cobalt LiMn2O4 that obtains granularity after tested is that 4-15 μ m is normal distribution, tap density 2.26g/cm
3。With material with carbon element as cooperating negative pole to make battery, under the room temperature that records first discharge capacity be 143mAh/g, 0.2C discharge 3.6V capacity accounts for total capacity 35%.The present invention is easy to control particle diameter and the distribution of product A, B, and can obtain the spherical nickel-cobalt lithium manganate material C of stay-in-grade high density, high power capacity and high discharge platform, is applicable to the stabilisation industrial production.
Claims (6)
1, a kind of preparation method of anode material lithium nickle cobalt manganic acid of lithium ion battery is characterized in that its process comprises the steps to form:
1), x:y:x promptly that the ratio of 2x+y=1 is mixed with the mixed solution that tenor is 40-100g/L with nickel salt, cobalt salt, manganese salt in molar ratio, 0.1≤x≤0.4,0.2≤y≤0.8 wherein, and satisfy 2x+y=1;
2), preparation contains the sodium hydroxide solution of 2mol-6mol/L and the ammonia spirit of 2-15mol/L;
3), will stir in the nickel cobalt-manganese salt mixed solution that prepare, sodium hydroxide solution, the continuous injecting reactor of ammonia spirit respectively, regulate the flow and the ratio of ammoniacal liquor flow of nickel cobalt-manganese salt mixed solution, control NH
3/ (Ni+Co+Mn) mol ratio is regulated the flow of sodium hydroxide solution simultaneously between 0.4-1.5, and the pH value in the control reactor remains between 8-11, and reactant liquor is discharged continuously from overfall;
4) add nitrogen, sulphite, nitrite, hydrazine water in the synthetic reaction with step 3), antioxidant is to prevent the oxidation in this course of reaction of manganese, cobalt;
5), product that step 3) reaction is discharged separates in solid-liquid separator, after washing gained solids to washings with water and reaching below the PH8.5, solids at 100-150 ℃, is dried and is obtained nickel cobalt manganese mixed hydroxides A after 1-2 hours;
6), the resulting nickel cobalt of step 5) manganese mixed hydroxides A put into sintering furnace between 300-500 ℃, carry out pre-burning, obtain the mixed oxide dry powder B of nickel manganese cobalt through the cooling sub-sieve;
7), nickel cobalt manganese mixed oxides B that step 6) is obtained, 10%-20% ethanolic solution, deionized water and place blender to mix through the lithium salts that milled processed is crossed to obtain slurry, the control charge ratio is Li/ (Ni+Co+Mn) mol ratio 1.03-1.08;
8), the slurry of step 7) placed to burn separates stove, be warming up to 800-1000 ℃ of insulation after 6-24 hour, be cooled to 400--600 ℃ of insulation cold quenching after 2-6 hour with the speed of 10 ℃-20 ℃ of per minutes again;
9), the product that step 8) is obtained obtains the spherical nickel-cobalt LiMn2O4 through pulverizing, sub-sieve.
2, the preparation method of a kind of anode material lithium nickle cobalt manganic acid of lithium ion battery according to claim 1, it is characterized in that, described nickel salt is selected from nickelous sulfate, nickel chloride or nickel nitrate, and cobalt salt is selected from cobaltous sulfate, cobalt chloride, cobalt nitrate, and manganese salt is selected from manganese sulfate, manganese chloride, manganese nitrate.
3, the preparation method of a kind of anode material lithium nickle cobalt manganic acid of lithium ion battery according to claim 1 is characterized in that, during the preparation of described mixed solution, the mol ratio of nickel and manganese remains the proportionate relationship of 1:1.
4, the preparation method of a kind of anode material lithium nickle cobalt manganic acid of lithium ion battery according to claim 1, it is characterized in that, after the product of described mixed solution is discharged reactor, adopt the liquid particles separation equipment, the particle diameter bigger particle separation of reaction in the resulting spherical nickel-cobalt manganese mixing hydrogen-oxygen thing come out to carry out subsequent treatment process, and particle diameter refills in the reactor than granule and grows up once more.
5, the preparation method of a kind of anode material lithium nickle cobalt manganic acid of lithium ion battery according to claim 1, it is characterized in that product nickel cobalt manganese mixed hydroxides A mixes with lithium salts by after forming cobalt-nickel-manganese oxide compound B 300-500 ℃ of pre-burnings again, sintering.
6, the preparation method of a kind of anode material lithium nickle cobalt manganic acid of lithium ion battery according to claim 5 is characterized in that, sintering is divided into following steps and constitutes:
First section: the mixture of cobalt-nickel-manganese oxide compound and lithium salts, directly be heated to 800-1100 ℃ after, be incubated 6-24 hours;
Second section: after cooling to 400--600 ℃ with 10 ℃/min behind the high temperature sintering, be incubated 2-6 hours;
The 3rd section: second section products therefrom obtained the spherical nickel-cobalt LiMn2O4 through cold quenching, pulverizing, sub-sieve.
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