CN102867952B - Method for preparing lithium-rich solid solution anode material by gas oxidation-coprecipitation method - Google Patents
Method for preparing lithium-rich solid solution anode material by gas oxidation-coprecipitation method Download PDFInfo
- Publication number
- CN102867952B CN102867952B CN201210388766.2A CN201210388766A CN102867952B CN 102867952 B CN102867952 B CN 102867952B CN 201210388766 A CN201210388766 A CN 201210388766A CN 102867952 B CN102867952 B CN 102867952B
- Authority
- CN
- China
- Prior art keywords
- lithium
- manganese
- nickel
- cobalt
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing a lithium-rich solid solution anode material by a gas oxidation-coprecipitation method. The preparation steps include weighing compounds of lithium, nickel, manganese and cobalt respectively according to lithium, nickel, manganese and cobalt ion molar ratio of (1+x):(1-x)*y: (x+z-x*z): (1-x)*k, mixing weighted wet-milling medium with the compounds of nickel, manganese and cobalt, feeding excessive oxidizing gas, simultaneously adding an alkali liquor, preparing a reacting mixing solution which contains precipitation by a wet mill in a wet-milling mode, subjecting the reacting mixing solution which contains the precipitation to aging, filtering and washing, mixing the reacting mixing solution with wet milling medium and the lithium compound, preparing a precursor by wet milling and drying, placing the precursor in air, an oxygen enrichment gas or pure oxygen atmosphere to prepare the lithium-rich solid solution anode material through sintering. The method for preparing the lithium-rich solid solution anode material by the gas oxidation-coprecipitation method has the advantages that the prepared electrode material is uniform in composition and has excellent electric discharging performance, and particularly the electric discharging cycle performance is excellent under the large current condition.
Description
Technical field
The invention belongs to technical field prepared by battery electrode material, be specifically related to a kind of method that oxidizing gas oxidizing process is prepared rich lithium solid solution cathode material of passing through that can be used for lithium battery, lithium ion battery, polymer battery and ultracapacitor.
Technical background
Spinel-type LiMn
2o
4have the features such as operating voltage is high, cheap, environmental friendliness, but the reversible capacity of this positive electrode is lower, a capacity of putting in the time of 1C rate charge-discharge only has 90-100mAh/g; At high temperature the discharge capacity of this positive electrode can decay fast with the carrying out of charge and discharge cycles.
Rich lithium solid solution cathode material Li
2mnO
3li[Ni
1/3co
1/3mn
1/3] O
2show that specific capacity is high, the advantage such as Heat stability is good, cycle performance are good, attracted domestic and international experts and scholars' height interest.The method that the rich lithium solid solution cathode material of preparation adopts at present comprises coprecipitation method, sol gel process, solid-phase sintering method etc.In these several preparation methods, in order further to improve and to prepare the chemical property of sample, as improve the current efficiency of the 1st circulation, improve the discharge performance of different multiplying electric current etc., also there is some doping preparation methods' research report.
In co-precipitation preparation method, be divided into again hydroxide coprecipitation step and carbonate coprecipitation method according to the difference of the precipitation generating.
In hydroxide coprecipitation step, according to adopting the difference of precipitation reagent can be divided into again lithium hydroxide coprecipitation method, NaOH (potassium) and ammoniacal liquor coprecipitation method, below discuss respectively:
Lithium hydroxide coprecipitation method is that employing LiOH is precipitation reagent, LiOH solution is added in the solution of manganese salt, nickel salt and cobalt salt, makes the compound of the precipitation of hydroxide of manganese, nickel and cobalt.By the compound washing of precipitation of hydroxide, dry after, mix with excessive LiOH, make rich lithium lithium manganate material [Guo X. et al. J. Power Sources, 2008,184:414 – 419. through one section or two sections or twice sintering; Denis Y. et al, J. Electrochem. Soc., 2010,157:A1177-A1182.; Li J., et al, J. Power Sources, 2011,196:4821 – 4825.].
In order to improve the multiplying power discharging property of sample prepared by lithium hydroxide coprecipitation method, the Li[Li that Wu Xiaobiao etc. prepare lithium hydroxide coprecipitation method
0.2mn
0.54ni
0.13co
0.13] O
2carry out carbon coated processing; Shi etc. are by the Li of preparation
1.048mn
0.381ni
0.286co
0.286o
2carry out magnetron sputtering processing, the positive electrode of preparation carbon coated.Result shows, carbon encapsulated material has high-rate discharge ability (5C, 145 mAh/g) [Wu Xiaobiao etc., Xiamen University's journal (natural science edition), 2008,47:224-227; Shi S. J. et al, Electrochim. Acta, 2012,63:112 – 117].
In order to improve the multiplying power discharging property of sample prepared by lithium hydroxide coprecipitation method, Croy etc. are by the Li of preparation
2mnO
3predecessor or Li
1.2mn
0.54co
0.13ni
0.13o
2and Li
1.13mn
0.47co
0.20ni
0.20o
2rich acid or acid salt processing for lithium solid-solution material, to improve performance [Croy J. R. et al, Electrochem. Commun., 2011,13:1063 – 1066.; Denis Y. et al, J. Electrochem. Soc., 2010,157: A1177-A1182.].Research shows, through (NH
4)
2sO
4the material of processing has higher capacity and good multiplying power discharging property.
In order further to improve the multiplying power discharging property of sample prepared by lithium hydroxide coprecipitation method, Rodrigues etc. add urea in the preparation, utilize urea decomposition product further to promote the generation of co-precipitation.Rodrigues etc. [Rodrigues I., Solid State Electrochem., 2012,16:1121 – 1132.] first prepare Co (NO
3)
26H
2o, Ni (NO
3)
26H
2o, Mn (NO
3)
26H
2o, NH
2cONH
2and LiOHH
2the mixed solution of O, adds NH
2cONH
2solution, has determined ureaclastic optimum temperature by hydro thermal method, microwave hydrothermal synthetic method or 100 DEG C of heatings.Research shows, along with the increase of reacting solution pH value, sediment is separated out from solution.After dry in air atmosphere, by synthetic the LiOH of dry hydroxide and excessive 3% LiNi
xmn
xco
(1 – 2x)o
2predecessor.After predecessor granulation, in air atmosphere respectively at 500 DEG C and 900 DEG C of sintering, last quench cooled.
NaOH (potassium) is to adopt the mixed solution of ammoniacal liquor and NaOH or KOH solution as precipitation reagent with ammoniacal liquor coprecipitation method, ammoniacal liquor and NaOH solution or ammoniacal liquor and KOH solution are added in manganese salt, nickel salt and cobalt salt solution, make the precipitation of the hydroxide of manganese, nickel and cobalt.Washing, after dry hydrogen oxide precipitation, with slightly excessive LiOH or the Li of stoichiometry
2cO
3mix, make rich lithium layered cathode material through double sintering.[Zhong Shengwen etc., power technology, 2012,36:59-62.; Urge the patent ZL200910264411.0 such as vertical peak]
In order further to improve the performance of sample prepared by NaOH (potassium) and By Ammonia Coprecipitation, Arunkumar etc. are by the rich lithium solid-solution material oxidant NO of preparation
2bF
4acetonitrile solution carry out chemical lithium deintercalation.[Arunkumar?T.?A.et?al,?Chem.?Mater.?2007,?19,?3067-3073.；?Wu?Y.?et?al,?J.?Power?Sources，?2008，?183：?749–754.]
In order to improve the performance of sample prepared by NaOH (potassium) and By Ammonia Coprecipitation, the rich lithium solid-solution material of the coated or doping of the preparation such as Wu.First prepare not coated sample by coprecipitation, then prepare surface by Al by solution route
2o
3, CeO
2, ZrO
2, SiO
2, ZnO, AlPO
4and F
-rich lithium solid-solution material (1-z) Li[Li of ion modification
1/3mn
2/3] O
2(z) Li[Mn
0.5 yni
0.5 yco
2y] O
2[Wu Y., Manthiram A., Solid State Ionics, 2009,180:50 – 56.].
Carbonate coprecipitation method is first to prepare the carbonate deposition of nickel, cobalt, manganese, and then mixes with lithium carbonate or lithium hydroxide, through double sintering method or one-stage sintering method or point one step preparation method, makes lithium-rich anode material.For example, in argon gas atmosphere, Liun etc. are by NH
4hCO
3, (NH
4)
2cO
3or Na
2cO
3solution adds NiSO
4, CoSO
4and MnSO
4mixed solution in, after filtration, washing, after dry Ni
0.2co
0.1mn
0.533(CO
3)
xpredecessor.Predecessor at 500 DEG C after sintering again with Li
2cO
3mix, obtain spherical powder Li at air atmosphere in 900 DEG C of sintering
1.167ni
0.2co
0.1mn
0.533o
2.Can reach 340mAh/g in 2.0 – 4.8 V voltage range discharge capacities.[Liun X. et al., Materials International, 2012,22:126 – 129.; Wang J. et al, Electrochim. Acta, 2012,66: 61 – 66.; Patent ZL201110300604.4].
In order further to improve coulombic efficiency and the discharge performance of the standby sample of carbonate coprecipitation legal system, carry out doping vario-property research.For example, Deng etc. is by nickelous sulfate, cobaltous sulfate, manganese sulfate solution and sodium carbonate liquor carbonate synthesis salt precursor (Ni
0.1875co
0.125mn
0.6875) CO
3.Precursor is suspended in to Al (NO
3)
39H
2in the O aqueous solution, drip NH
4f suspension, process stirs, and after being dried with 100 DEG C after filtering, sintering at 400 DEG C, prepares 2wt% AlF
3coated Li
1.1ni
0.15co
0.1mn
0.55o
1.95.This material reaches 304 mAh/g at the reversible capacity of 55 DEG C, and the coulombic efficiency of circulation reaches 84% first.[Deng?B.H.?et?al,?J.?Electrochem.?Soc.,?2010，157：A1035-A1039.]
In order further to improve the discharge performance of the standby sample of carbonate coprecipitation legal system, carry out preparation research step by step.Shin etc. react cobaltous sulfate, manganese sulfate with ammonium bicarbonate soln, make Co
0.5mn
0.5cO
3precursor.The dry rear and Li of this precursor
2cO
3mechanical mixture.In air atmosphere, make 0.5Li respectively at 550 DEG C and 850 DEG C of sintering
2mnO
30.5LiCoO
2predecessor.This predecessor is mixed with ammonium dihydrogen phosphate, glycolic, nickel nitrate, lithium nitrate, dry in air atmosphere, then at 550 DEG C sintering, make 0.5Li
2mnO
30.5LiNi
0.44co
0.25mn
0.31o
2[Shin, C. et al, J. Electrochem. Soc., 2012,159: A121-A127.].
In above-mentioned preparation process, due to by co-precipitation preparation method, no matter be the coprecipitation that forms the coprecipitation of hydroxide or form carbonate, all will be through a precipitation, washing precipitation and dry process while being prepared.While utilizing hydroxide coprecipitation step to be prepared, the manganous hydroxide generating due to course of reaction is very easily oxidized by oxygen in air or oxygen soluble in water, cobalt hydroxide also can be oxidized by oxygen in air or oxygen soluble in water (the chief editor of Wuhan University under certain condition, analytical chemistry (the 2nd edition), Higher Education Publishing House, October nineteen eighty-two, Beijing: the 14th page to the 17th page).In the time using ammoniacal liquor as precipitation reagent, excess ammonia is reacted the Co (NH generating with cobalt ions
3)
6 2+ion can be oxidized by oxygen in air (the chief editor of Wuhan University, analytical chemistry (the 2nd edition), Higher Education Publishing House, October nineteen eighty-two, Beijing: the 14th page to the 17th page), therefore, when forefathers utilize hydroxide coprecipitation step to prepare, the predecessor of sintering is the compound of manganic and bivalent manganese, even contains trivalent cobalt and cobaltous compound.Due in preparing under environment of not controlling, this oxidizing process not exclusively.The ratio of trivalent ion and divalent ion amount of substance changes along with factors such as preparation time, preparation temperature, stirrings.Research shows, in the rich lithium solid-solution material of preparation, mixing phenomenon usually occurs for different lithium position, manganese position and nickel position ion, has a strong impact on the chemical property of preparing sample.In order to address this problem, in preparation when precipitation of hydroxide, have document to adopt the method for nitrogen protection precipitation, but, the method for nitrogen protection precipitation can only deaeration in the impact of oxygen, cannot get rid of the impact of oxygen soluble in water.In order to address this problem, the present invention adds oxidant in reaction mixture, the manganous hydroxide complete oxidation that preparation process is generated is MnOOH, is manganic (MnOOH) and the reacting of the compound of the hydroxide of nickel and cobalt time prepared by sintering.Therefore the sample that, prepared by method of the present invention has unique chemical property.
The present invention also can avoid common solid sintering technology to mix by the simple ball milling of product, then carry out reactant that technique prepared by sintering exists mix inhomogeneous, the problem such as the consistency of the chemical property of product is poor.
Summary of the invention
Gas oxidation-coprecipitation is prepared the method for rich lithium solid solution cathode material, it is characterized in that preparation process is made up of following steps:
(1) be (1+x): (1-x) y: (x+z-xz) according to lithium ion, nickel ion, manganese ion, cobalt ions mol ratio: (1-x) k takes respectively the compound of lithium, compound, the compound of manganese and the compound of cobalt of nickel; The span of x, y, z and k meets following relation simultaneously: 0.15≤x≤0.60, and 0.05≤y≤0.45,0.125≤z≤0.75,0.05≤k≤0.45 ,-0.1≤
(2y-2xy+3x+4 z-4xz+3k-3x k-3) ≤ 0.1; Reactant cumulative volume is the summation of compound, the compound of manganese and the compound volume of cobalt of compound, the nickel of lithium; Measure two parts of wet grinding media according to the volume ratio of reactant cumulative volume and wet grinding media in 1:0.5～10 scope.
(2), 40 DEG C to 95 DEG C temperature ranges, compound, the compound of manganese and the compound of cobalt by a wet grinding media measuring with the nickel taking, obtain mixed solution.Pass into excess of oxygen voltinism gas in mixed solution in, add alkali lye, prepare and comprise sedimentary reaction mixture with wet milk wet-milling.Wherein, the wet-milling time, between 0.50 hour～10 hours, adds alkali lye to make the acidity that comprises sedimentary reaction mixture
pH is 10 to 14 between, the trivalent sediment that to pass into divalence sediment complete oxidation that excess of oxygen voltinism gas makes to comprise manganese in sedimentary reaction mixture be manganese.To comprise sedimentary reaction mixture 40 DEG C to 95 DEG C ageings 2 hours to 24 hours, filter and wash and remove water-soluble ion with distilled water or deionized water, by the compound of the filter residue of acquisition, another part of wet grinding media measuring and lithium, with wet milk wet-milling 1 hour～24 hours
make predecessor 1 ,
by predecessor 1 prepare dry predecessor 2 with heating and drying method.Predecessor 2 is placed in to air
, in oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 DEG C～550 DEG C of temperature ranges 3 hours～15 hours, then be placed in air, oxygen rich gas or pure oxygen atmosphere in arbitrary temperature sintering of 800 DEG C～1050 DEG C of temperature ranges 3 hours～24 hours, prepare rich lithium solid solution cathode material.
Described oxidizing gas is air, oxygen, ozone, chlorine, fluorine gas, nitrogen dioxide or phosgene, or the mist of above two kinds of oxidizing gas arbitrary volume ratios.
The compound of described lithium is lithium hydroxide, lithium oxalate, lithium nitrate, lithium carbonate, lithium sulfate, lithium acetate, lithium citrate, lithium formate, lithium iodide, lithium chloride or lithia.
The compound of described nickel is nickel hydroxide, nickel oxalate, nickel nitrate, nickelous carbonate, citric acid nickel, basic nickel carbonate, nickel acetate, nickel formate or nickel chloride.
The compound of described manganese is manganese oxalate, manganese nitrate, manganese sulfate, manganese acetate, formic acid manganese or manganese chloride.
The compound of described cobalt is cobalt hydroxide, cobalt oxalate, cobalt nitrate, cobalt carbonate, citric acid cobalt, basic cobaltous carbonate, cobalt acetate, cobaltous formate or cobalt chloride.
Described heating and drying method is that vacuumize or spraying are dry or normal heating is dry; Described vacuumize is the arbitrary temperature 80 DEG C～280 DEG C of temperature ranges by predecessor 1, dry between 10Pa～10132Pa vacuum under pressure, prepares predecessor 2; Described spraying is dry is the arbitrary temperature 110 DEG C～280 DEG C of temperature ranges,
by predecessor 1 adopt spray dryer to prepare dry predecessor 2.Described normal heating is dry is the arbitrary temperature heat drying 150 DEG C～280 DEG C of temperature ranges by predecessor 1, prepares predecessor 2.
Described wet grinding media is deionized water or distilled water, or ethanol, methyl alcohol or formaldehyde and deionized water or distilled water volume ratio are at the solution of 10:1～100 scope.
Described oxygen rich gas is that oxygen volume content is greater than 21% and be less than the gas of 100% scope.
Described aqueous alkali is that the weight ratio of lithium hydroxide, NaOH or potassium hydroxide and water is at the mixed liquor of 1:1～10 scope; Described water is distilled water or deionized water.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Brief description of the drawings
Fig. 1 be the sample prepared of the embodiment of the present invention 1 at 2.5 to 4.6V voltage ranges, the discharge curve of the 1st circulation under 1.5C multiplying power electric current.
Fig. 2 is the XRD diffraction pattern of the sample prepared of the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed.Embodiment further supplements and explanation of the present invention, instead of to the restriction of inventing.
Embodiment 1
It is 1.15: 0.0425: 0.4543 according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions: 0.3825 takes respectively lithium hydroxide, nickel hydroxide, manganese acetate, cobalt hydroxide.Reactant cumulative volume is the summation of lithium hydroxide, nickel hydroxide, manganese acetate and cobalt hydroxide volume.Be that 1:10 measures two parts of deionized waters (being equivalent to (2 (1-x) y+4 (x+z-xz)+3 (1-x) k-x-3)=-0.10 of summary of the invention part) according to reactant cumulative volume and deionized water volume ratio.
At 40 DEG C, a deionized water measuring and the nickel hydroxide, manganese acetate and the cobalt hydroxide that take are mixed to get to mixed solution; In mixed solution, pass into the alkali lye that adds lithium hydroxide and water weight ratio 1:1 in excess air, comprise sedimentary reaction mixture with wet milk wet-milling preparation in 0.50 hour.Wherein, add alkali lye until the acidity that comprises sedimentary reaction mixture is pH 10, the trivalent sediment that to pass into divalence sediment complete oxidation that excess air makes to comprise manganese in sedimentary reaction mixture be manganese.To comprise the ageing 2 hours at 40 DEG C of sedimentary reaction mixture, filter and wash and remove water-soluble ion with distilled water, the lithium hydroxide of the filter residue of acquisition, another part of deionized water measuring and weighing is mixed, with wet milk wet-milling 1 hour, be dried in 10Pa vacuum under pressure at 80 DEG C, obtain predecessor 2; Predecessor 2 is placed in to air atmosphere, 300 DEG C of sintering 3 hours, is then placed in 1050 DEG C of sintering 24 hours, preparation consists of 0.15 Li
2mnO
30.85 Li[Ni
0.05mn
0.358co
0.45] O
2rich lithium solid solution cathode material.The discharge capacity of preparing sample the 1st circulation under 1.5C multiplying power electric current is 130mAh/g.As shown in Figure 1, the XRD diffraction pattern of the sample of preparation as shown in Figure 2 for the discharge curve of the 1st circulation.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Embodiment 2
Be 1.60:0.18 according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions: respectively take lithium nitrate, nickel oxalate, manganese sulfate, cobalt chloride (being equivalent to (2 (1-x) y+4 (x+z-xz)+3 (1-x) k-x-3)=-0.10 of summary of the invention part) at 0.65: 0.18.The cumulative volume of reactant is the summation of lithium nitrate, nickel oxalate, manganese sulfate and cobalt chloride volume, is that 1:0.5 measures two parts of ethanol waters according to reactant cumulative volume and ethanol water volume ratio.In ethanol water, the volume ratio of ethanol and deionized water is 10:1.
At 95 DEG C, a ethanol water measuring and the nickel oxalate, manganese sulfate, the cobalt chloride that take are mixed to get to mixed solution.In mixed solution, pass into the alkali lye that adds lithium hydroxide and distilled water weight ratio 1:10 in excessive ozone gas, with wet milk wet-milling 10 hours, preparation comprised sedimentary reaction mixture.Wherein, add alkali lye to make the acidity that comprises sedimentary reaction mixture reach pH 14, the trivalent sediment that to pass into divalence sediment complete oxidation that excessive ozone gas makes to comprise manganese in sedimentary reaction mixture be manganese.To comprise sedimentary reaction mixture 95 DEG C of ageings 24 hours, filter and wash and remove water-soluble ion with deionized water, the lithium nitrate of the filter residue of acquisition, another part of ethanol water measuring and weighing is mixed, with wet milk wet-milling 24 hours, be dried with spray dryer at 110 DEG C, make predecessor 2.Predecessor 2 is placed in to the oxygen-enriched air atmosphere of oxygen volume content 99%, 550 DEG C of sintering 15 hours, then is placed in 800 DEG C of sintering 3 hours, preparation consists of 0.60 Li
2mnO
30.40 Li[Ni
0.45mn
0.125co
0.45] O
2rich lithium solid solution cathode material.Preparing sample discharge capacity under 1C multiplying power electric current is 170mAh/g.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Embodiment 3
Be 1.6 according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions: 0.02:0.90: 0.02 takes respectively lithium iodide, nickel nitrate, manganese oxalate, cobalt oxalate; Reactant cumulative volume is the summation of lithium iodide, nickel nitrate, manganese oxalate and cobalt oxalate volume, is that 1:2 measures two parts of methanol aqueous solutions (being equivalent to (2 (1-x) y+4 (x+z-xz)+3 (1-x) k-x-3)=0.10 of summary of the invention part) according to reactant cumulative volume and methanol aqueous solution volume ratio.In methanol aqueous solution, the volume ratio of methyl alcohol and deionized water is 1:10.
At 50 DEG C, a methanol aqueous solution measuring and the nickel nitrate, manganese oxalate, the cobalt oxalate that take are mixed to get to mixed solution.In mixed solution, pass into fluorine gas with volume of air than the excessive mist of 1:100, add the alkali lye of NaOH and deionized water weight ratio 1:5 simultaneously, with wet milk wet-milling 5 hours, preparation comprised sedimentary reaction mixture.Wherein, add alkali lye to make the acidity that comprises sedimentary reaction mixture reach pH 11, the trivalent sediment that to pass into divalence sediment complete oxidation that fluorine gas and volume of air make to comprise manganese in sedimentary reaction mixture than the excessive mist of 1:100 be manganese.To comprise sedimentary reaction mixture 65 DEG C of ageings 12 hours, filter and wash and remove water-soluble ion with distilled water, the lithium iodide of the filter residue of acquisition, another part of methanol aqueous solution measuring and weighing is mixed, with wet milk wet-milling 12 hours, dry with spray dryer at 280 DEG C, prepare dry predecessor 2.Predecessor 2 is placed in to pure oxygen atmosphere, 550 DEG C of sintering 5 hours, is then placed in 850 DEG C of sintering 3 hours, preparation consists of 0.60 Li
2mnO
30.40 Li[Ni
0.05mn
0.75co
0.05] O
2rich lithium solid solution cathode material.Preparing sample discharge capacity under 1C multiplying power electric current is 136mAh/g.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Embodiment 4
It is 1.15: 0.3825: 0.32 according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions: 0.3825 takes respectively lithia, nickel acetate, manganese oxalate, cobalt chloride.Reactant cumulative volume is the summation of lithia, nickel acetate, manganese oxalate and cobalt chloride volume, measures two parts of formalins (being equivalent to (2 (1-x) y+4 (x+z-xz)+3 (1-x) k-x-3)=0.043 of summary of the invention part) according to reactant cumulative volume and formalin volume ratio 1:10.In formalin, the volume ratio of formaldehyde and distilled water is 1:1.
At 80 DEG C, a formalin measuring and the nickel acetate, manganese oxalate and the cobalt chloride that take are mixed to get to mixed solution; In mixed solution, pass into the alkali lye that adds NaOH and deionized water weight ratio 1:2 in excessive chlorine, comprise sedimentary reaction mixture with wet milk wet-milling preparation in 8 hours.Wherein, add alkali lye to make the acidity that comprises sedimentary reaction mixture reach pH 13, the trivalent sediment that to pass into divalence sediment complete oxidation that excessive chlorine makes to comprise manganese in sedimentary reaction mixture be manganese.To comprise sedimentary reaction mixture 80 DEG C of ageings 11 hours, filter and wash and remove water-soluble ion with distilled water, the lithia of the filter residue of acquisition, another part of formalin measuring and weighing is mixed, wet-milling 24 hours, be dried in 10132 Pa vacuum under pressure at 280 DEG C, prepare dry predecessor 2; Predecessor 2 is placed in to air atmosphere, 450 DEG C of sintering 10 hours, then is placed in 1000 DEG C of sintering 20 hours, preparation consists of 0.15 Li
2mnO
30.85 Li[Ni
0.45mn
0.20co
0.45] O
2rich lithium solid solution cathode material.Preparing sample discharge capacity under 1C multiplying power electric current is 131mAh/g.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Embodiment 5
It is 1.6: 0.112: 0.804 according to lithium ion, nickel ion, manganese ion, cobalt ions mol ratio: 0.04: take respectively lithium oxalate, nickel acetate, manganese nitrate, cobalt nitrate; Reactant cumulative volume is the summation of lithium oxalate, nickel acetate, manganese nitrate and cobalt nitrate volume.Be respectively 1:1 and 1:5 measures two parts of distilled water according to reactant cumulative volume and distilled water volume ratio, be called distilled water 1 and distilled water 2 (being equivalent to (2 (1-x) y+4 (x+z-xz)+3 (1-x) k-x-3)=-0.04 of summary of the invention part).
At 95 DEG C, the distilled water measuring 1 and the nickel acetate, manganese nitrate and the cobalt nitrate that take are mixed to get to mixed solution.In mixed solution, pass into the excessive gaseous mixture that chlorine and volume of air ratio are 100:1, add the alkali lye of NaOH and distilled water weight ratio 1:10 simultaneously, prepare and comprise sedimentary reaction mixture with wet milk wet-milling.With wet milk wet-milling 5 hours, add alkali lye to make the acidity that comprises sedimentary reaction mixture reach pH 11, pass into the trivalent sediment that chlorine and volume of air are manganese than the divalence sediment complete oxidation that makes to comprise manganese in sedimentary reaction mixture for the excessive gaseous mixture of 1:1.To comprise sedimentary reaction mixture 55 DEG C of ageings 20 hours, filter and wash and remove water-soluble ion with distilled water, the lithium oxalate of the filter residue of acquisition, the distilled water 2 measuring and weighing is mixed, with wet milk wet-milling 2 hours, 280 DEG C of vacuumizes under 101Pa, prepare predecessor 2; Predecessor 2 is placed in to oxygen volume and accounts for 30% oxygen-enriched air gas atmosphere, 450 DEG C of sintering 3 hours, be then placed in oxygen volume and account for 70% oxygen-enriched air gas atmosphere in 820 DEG C of sintering 24 hours, make and consist of 0.60 Li
2mnO
30.40 Li[Ni
0.28mn
0.51co
0.10] O
2rich lithium solid solution cathode material.Preparing sample discharge capacity under 1C multiplying power electric current is 162mAh/g.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Embodiment 6
It is 1.3: 0.189: 0.5947 according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions: 0.21 takes respectively lithium acetate, nickel acetate, manganese chloride and cobalt carbonate.The cumulative volume of reactant is the summation of lithium acetate, nickel acetate, manganese chloride and cobalt carbonate volume, be respectively 1:1 and 1:5 measures two parts of ethanol waters according to reactant cumulative volume and ethanol water volume ratio, be called ethanol water 1 and ethanol water 2 (being equivalent to (2 (1-x) y+4 (x+z-xz)+3 (1-x) k-x-3)=0.087 of summary of the invention part).In ethanol water, the volume ratio of ethanol and deionized water is 1:1.
At 60 DEG C, the ethanol water measuring 1 and nickel acetate, manganese chloride and cobalt carbonate are mixed to get to mixed solution.In mixed solution, pass into the excessive gaseous mixture that oxygen and ozone volume ratio are 1:10, add the alkali lye of potassium hydroxide and deionized water weight ratio 1:1 simultaneously, within 3 hours, prepare and comprise sedimentary reaction mixture with wet milk wet-milling.Wherein, add the mixed liquor of potassium hydroxide and deionized water weight ratio 1:1 to make the acidity that comprises sedimentary reaction mixture reach pH 10, the trivalent sediment that to pass into divalence sediment complete oxidation that excessive gaseous mixture that oxygen and ozone volume ratio are 1:10 makes to comprise sedimentary reaction mixture manganese be manganese.To comprise sedimentary reaction mixture 95 DEG C of ageings 2 hours, filter and wash and remove water-soluble ion with deionized water, the lithium acetate of the filter residue of acquisition, the ethanol water 2 measuring and weighing is mixed, and wet-milling is dried under normal pressure at 150 DEG C for 24 hours, prepares predecessor 2; Predecessor 2 is placed in to oxygen volume and accounts for 50% oxygen-enriched air atmosphere, 450 DEG C of sintering 12 hours, be then placed in oxygen volume and account for 99% oxygen-enriched air gas atmosphere in 850 DEG C of sintering 24 hours, preparation consists of 0.30 Li
2mnO
30.70 Li[Ni
0.27mn
0.421co
0.30] O
2rich lithium solid solution cathode material.Preparing sample discharge capacity under 1C multiplying power electric current is 139mAh/g.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Embodiment 7
It is 1.40: 0.075: 0.70 according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions: 0.18 takes respectively lithia, nickel formate, manganese chloride and cobalt carbonate.The cumulative volume of reactant is the summation of lithia, nickel formate, manganese chloride and cobalt carbonate volume, be respectively 1:2 and 1:5 measures two parts of methanol aqueous solutions according to reactant cumulative volume and methanol aqueous solution volume ratio, be called methanol aqueous solution 1 and methanol aqueous solution 2 (being equivalent to (2 (1-x) y+4 (x+z-xz)+3 (1-x) k-x-3)=0.090 of summary of the invention part).In ethanol water, the volume ratio of ethanol and deionized water is 1:1.
At 60 DEG C, the methanol aqueous solution measuring 1 and the nickel formate, manganese chloride and the cobalt carbonate that take are mixed to get to mixed solution.In mixed solution, pass into excessive nitrogen dioxide gas, add the alkali lye of potassium hydroxide and distilled water weight ratio 1:1 simultaneously, with wet milk wet-milling 5 hours, preparation comprised sedimentary reaction mixture.Wherein, add alkali lye to make the acidity that comprises sedimentary reaction mixture reach pH 14, the trivalent sediment that to pass into divalence sediment complete oxidation that excessive nitrogen dioxide makes to comprise manganese in sedimentary reaction mixture be manganese.To comprise the ageing 24 hours at 50 DEG C of sedimentary reaction mixture, filter and remove water-soluble ion with deionized water washing, the lithia of the filter residue of acquisition, the methanol aqueous solution 2 measuring and weighing being mixed to wet-milling 7 hours, be dried under normal pressure at 280 DEG C, prepare predecessor 2; Predecessor 2 is placed in to oxygen volume and accounts for 60% oxygen-enriched air gas atmosphere, 550 DEG C of sintering 12 hours, be then placed in oxygen volume and account for 60% oxygen-enriched air gas atmosphere in 850 DEG C of sintering 24 hours, preparation consists of 0.40 Li
2mnO
30.60 Li[Ni
0.125mn
0.50co
0.30] O
2rich lithium solid solution cathode material.Preparing sample discharge capacity under 1C multiplying power electric current is 191mAh/g.
Compared with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, consuming time few, and the electrode material composition of preparation evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Claims (10)
1. gas oxidation-coprecipitation is prepared the method for rich lithium solid solution cathode material, it is characterized in that preparation process is made up of following steps:
(1) be (1+x): (1-x) y: (x+z-xz) according to lithium ion, nickel ion, manganese ion, cobalt ions mol ratio: (1-x) k takes respectively the compound of lithium, compound, the compound of manganese and the compound of cobalt of nickel; The span of x, y, z and k meets following relation simultaneously: 0.15≤x≤0.60,0.05≤y≤0.45,0.125≤z≤0.75,0.05≤k≤0.45 ,-0.1≤(2y-2xy+3x+4 z-4xz+3k-3x k-3)≤0.1; Reactant cumulative volume is the volume summation of compound, the compound of manganese and the compound of cobalt of compound, the nickel of lithium; Measure two parts of wet grinding media according to the volume ratio of reactant cumulative volume and wet grinding media in 1:0.5～10 scope;
(2), 40 DEG C to 95 DEG C temperature ranges, a wet grinding media measuring and compound, the compound of manganese and the compound of cobalt of the nickel taking are obtained to mixed solution; Pass into excess of oxygen voltinism gas in mixed solution in, add alkali lye, use wet milk wet-milling, preparation comprises sedimentary reaction mixture; Wherein, the wet-milling time is between 0.50 hour～10 hours, add alkali lye to make the acidity pH that comprises sedimentary reaction mixture between 10 to 14, the trivalent sediment that to pass into divalence sediment complete oxidation that excess of oxygen voltinism gas makes to comprise manganese in sedimentary reaction mixture be manganese; To comprise sedimentary reaction mixture 40 DEG C to 95 DEG C ageings 2 hours to 24 hours, filter and wash and remove water-soluble ion with distilled water or deionized water, by the compound of the filter residue of acquisition, another part of wet grinding media measuring and lithium, within 1 hour～24 hours, make predecessor 1 with wet milk wet-milling, predecessor 1 use heating and drying method is prepared to dry predecessor 2; Predecessor 2 is placed in to air
, in oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 DEG C～550 DEG C of temperature ranges 3 hours～15 hours, then be placed in air, oxygen rich gas or pure oxygen atmosphere in arbitrary temperature sintering of 800 DEG C～1050 DEG C of temperature ranges 3 hours～24 hours, prepare rich lithium solid solution cathode material.
2. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that described oxidizing gas is air, oxygen, ozone, chlorine, fluorine gas, nitrogen dioxide or phosgene, or the mist of above two kinds of oxidizing gas arbitrary volume ratios.
3. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that the compound of described lithium is lithium hydroxide, lithium oxalate, lithium nitrate, lithium carbonate, lithium sulfate, lithium acetate, lithium citrate, lithium formate, lithium iodide, lithium chloride or lithia.
4. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that the compound of described nickel is nickel hydroxide, nickel oxalate, nickel nitrate, nickelous carbonate, citric acid nickel, basic nickel carbonate, nickel acetate, nickel formate or nickel chloride.
5. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that the compound of described manganese is manganese oxalate, manganese nitrate, manganese sulfate, manganese acetate, formic acid manganese or manganese chloride.
6. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that the compound of described cobalt is cobalt hydroxide, cobalt oxalate, cobalt nitrate, cobalt carbonate, citric acid cobalt, basic cobaltous carbonate, cobalt acetate, cobaltous formate or cobalt chloride.
7. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that described heating and drying method is that vacuumize or spraying are dry or normal heating is dry; Described vacuumize is the arbitrary temperature 80 DEG C～280 DEG C of temperature ranges by predecessor 1, dry between 10Pa～10132Pa vacuum under pressure, prepares predecessor 2; Described spraying is dry is the arbitrary temperature 110 DEG C～280 DEG C of temperature ranges, adopts spray dryer to prepare dry predecessor 2 predecessor 1; Described normal heating is dry is the arbitrary temperature heat drying 150 DEG C～280 DEG C of temperature ranges by predecessor 1, prepares predecessor 2.
8. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that described wet grinding media is deionized water or distilled water, or ethanol, methyl alcohol or formaldehyde and deionized water or distilled water volume ratio are at the solution of 10:1～100 scope.
9. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that described oxygen rich gas is that oxygen volume content is greater than 21% and be less than the gas of 100% scope.
10. gas oxidation-coprecipitation according to claim 1 is prepared the method for rich lithium solid solution cathode material, it is characterized in that described alkali lye is that the weight ratio of lithium hydroxide, NaOH or potassium hydroxide and water is at the mixed liquor of 1:1～10 scope; Described water is distilled water or deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210388766.2A CN102867952B (en) | 2012-10-15 | 2012-10-15 | Method for preparing lithium-rich solid solution anode material by gas oxidation-coprecipitation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210388766.2A CN102867952B (en) | 2012-10-15 | 2012-10-15 | Method for preparing lithium-rich solid solution anode material by gas oxidation-coprecipitation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102867952A CN102867952A (en) | 2013-01-09 |
| CN102867952B true CN102867952B (en) | 2014-11-26 |
Family
ID=47446658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210388766.2A Active CN102867952B (en) | 2012-10-15 | 2012-10-15 | Method for preparing lithium-rich solid solution anode material by gas oxidation-coprecipitation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102867952B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996820A (en) * | 2014-05-30 | 2014-08-20 | 南京安普瑞斯有限公司 | Lithium ion battery as well as mixed positive electrode and active material with synergistic effect |
| CN107256959B (en) * | 2017-07-05 | 2019-10-22 | 天津巴莫科技股份有限公司 | The preparation method of rich oxidate for lithium solid-solution material |
| CN110482611A (en) * | 2019-09-06 | 2019-11-22 | 辽宁星空钠电电池有限公司 | A kind of method that rapid precipitation prepares alkaline oxygenated manganese nanometer sheet self assembled three-dimensional ball |
| TWI800941B (en) * | 2021-10-06 | 2023-05-01 | 芯量科技股份有限公司 | Method of manufacturing a uniform cathode material precursor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244237B (en) * | 2011-06-10 | 2016-08-03 | 北京理工大学 | A kind of synthetic method of anode material for lithium ion battery with high power capacity |
| CN102544475B (en) * | 2012-03-07 | 2015-06-17 | 湖北万润新能源科技发展有限公司 | Method for preparing lithium-enriched lithium manganese oxide solid solution cathode material |
-
2012
- 2012-10-15 CN CN201210388766.2A patent/CN102867952B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102867952A (en) | 2013-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102881891B (en) | Method for preparing trivalent ion-doped lithium-rich solid solution cathode material | |
| CN102881874B (en) | Method for preparing lithium-rich solid solution cathode material through reduction | |
| CN103904311B (en) | Lithium-rich manganese-based anode material that a kind of surface is coated compound and preparation method thereof | |
| CN102916169B (en) | Lithium-rich manganese-based anode material and method for manufacturing same | |
| CN102881879B (en) | Method for preparing lithium-rich solid solution cathode material through gas oxidation and acid solution combined treatment | |
| CN109336193A (en) | Multielement original position codope ternary material precursor and its preparation method and application | |
| CN102881894B (en) | Method for preparing lithium-enriched solid solution cathode material by doping iron, copper and tin ions | |
| CN108767239A (en) | A kind of nickelic low cobalt tertiary cathode material and preparation method thereof | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN102875130B (en) | Method for preparing doped lithium-enriched solid solution cathode material by using carbon-added compound | |
| CN105118983B (en) | Method for preparing lithium nickel manganese oxide anode material | |
| CN105692721B (en) | A kind of sodium-ion battery positive material and preparation method thereof and application method | |
| CN102306765A (en) | Preparation method for nickel-manganese-cobalt anode material of lithium ion battery | |
| CN104134797B (en) | A kind of high-capacity lithium-rich cathode material and preparation method thereof | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN104835957B (en) | Preparation method of high-nickel ternary material used for lithium ion battery | |
| CN102881875B (en) | Method for preparing lithium-rich solid solution cathode material doped with divalent ions through partial dissolution | |
| CN102881876B (en) | Method for preparing lithium-rich solid solution cathode material through reduction co-precipitation | |
| CN102881889B (en) | Method for preparing lithium-enriched solid solution cathode material by two-section direct temperature-rise sintering | |
| CN102881878B (en) | Method for preparing lithium-rich solid solution cathode material by virtue of metal reduction process | |
| CN102867952B (en) | Method for preparing lithium-rich solid solution anode material by gas oxidation-coprecipitation method | |
| CN102881880B (en) | Method for preparing monovalent ion-doped lithium-rich solid solution cathode material by partial dissolution method | |
| CN102881890B (en) | Method for preparing lithium-rich solid solution cathode material through oxidizing gas oxidation | |
| CN102881877B (en) | Method for preparing lithium-rich solid solution positive pole material by carbon added compounds | |
| CN103594704A (en) | Preparation method for tetravalent titanium ion-doped spinel lithium-rich lithium manganate positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170608 Address after: 363000 North Zone, Capital Industrial Zone, Zhaoan County, Zhangzhou, Fujian Patentee after: Fujian dynavolt Amperex Technology Limited Address before: Minhou County of Fuzhou City, Fujian province 350108 street town of Qishan campus of Fujian Normal University Department of science and technology Patentee before: Fujian Normal University |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20181217 Granted publication date: 20141126 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20211217 Granted publication date: 20141126 |