CN102881880A - Method for preparing monovalent ion-doped lithium-rich solid solution cathode material by partial dissolution method - Google Patents
Method for preparing monovalent ion-doped lithium-rich solid solution cathode material by partial dissolution method Download PDFInfo
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Abstract
The invention relates to a method for preparing a monovalent ion-doped lithium-rich solid solution cathode material by a partial dissolution method. The method is characterized by respectively weighing a lithium compound, a nickel compound, a manganese compound, a cobalt compound and an M compound according to the molar ratio of lithium ion to nickel ion to manganese ion to cobalt ion to M ion of (1.1+0.90*x):(1-x)*y:(x+z-x*z):(1-x)*k:(1-x)*q, mixing the nickel compound, the manganese compound, the cobalt compound and the M compound, adding a wet grinding medium and an organic weak acid into the mixture, performing wet grinding and mixing the materials, adding the lithium compound into the mixture, performing wet grinding on the mixture to obtain a precursor 1, drying the precursor 1, placing the precursor 1 in air, oxygen-enriched gas or a pure oxygen atmosphere, and performing a two-section sintering method or two-time sectional sintering method to prepare the lithium-rich solid solution cathode material. The cathode material prepared by the method is uniform in components and excellent in discharge performance and particularly cycle performance of discharge under a high-current condition.
Description
Technical field
The invention belongs to the technical field of battery electrode material preparation, be specifically related to a kind of preparation method who can be used for the rich lithium solid solution cathode material of doping of lithium battery, lithium ion battery, polymer battery and ultracapacitor.
Technical background
Spinel-type LiMn
2O
4Have the characteristics such as operating voltage height, cheap, environmental friendliness, but the reversible capacity of this positive electrode is lower, a capacity of putting when the 1C rate charge-discharge only has 90-100mAh/g; At high temperature the discharge capacity of this positive electrode can decay fast along 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 the advantages such as specific capacity height, Heat stability is good, cycle performance be good, thereby attracted domestic and international experts and scholars' height interest.The method of the rich lithium solid solution cathode material employing of at present preparation comprises coprecipitation method, sol gel process, solid-phase sintering method etc.In these several preparation methods, for the further chemical property that improves the preparation sample, as improve the current efficiency of the 1st circulation, improve the discharge performance of different multiplying electric current etc., some doping preparation methods' research report is also arranged.
In co-precipitation preparation method, the difference of the precipitation that foundation generates is divided into again hydroxide coprecipitation step and carbonate coprecipitation method.
In hydroxide coprecipitation step, can be divided into again lithium hydroxide coprecipitation method, NaOH (potassium) and ammoniacal liquor coprecipitation method according to the difference that adopts precipitation reagent, below discuss respectively:
The 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.After the washing of the compound of precipitation of hydroxide, drying, 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.].
For the multiplying power discharging property of the sample that improves lithium hydroxide coprecipitation method preparation, Wu Xiaobiao etc. are with the Li[Li of lithium hydroxide coprecipitation method preparation
0.2Mn
0.54Ni
0.13Co
0.13] O
2Carrying out carbon coated processes; Shi etc. are with the Li of preparation
1.048Mn
0.381Ni
0.286Co
0.286O
2Carry out magnetron sputtering and process, the positive electrode of preparation carbon coated.The result shows that 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].
For the multiplying power discharging property of the sample that improves lithium hydroxide coprecipitation method preparation, Croy etc. are with 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 lithium solid-solution material is processed with acid or acid salt, 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.].Studies show that, through (NH
4)
2SO
4The material of processing has higher capacity and good multiplying power discharging property.
For the multiplying power discharging property of the sample that further improves lithium hydroxide coprecipitation method preparation, Rodrigues etc. add urea in the preparation, utilize the urea decomposition product further to promote the generation of co-precipitation.Rodrigues etc. [Rodrigues I., Solid State Electrochem., 2012,16:1121 – 1132.] prepare first 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 been determined ureaclastic optimum temperature with hydro thermal method, microwave hydrothermal synthetic method or 100 ℃ of heatings.Studies show that along with the increase of reacting solution pH value, sediment is separated out from solution.In air atmosphere, after the drying, the hydroxide of drying and excessive 3% LiOH are synthesized LiNi
xMn
xCo
(1 – 2x)O
2Predecessor.After the predecessor granulation, in air atmosphere respectively at 500 ℃ and 900 ℃ 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 the ammoniacal liquor coprecipitation method, in ammoniacal liquor and NaOH solution or ammoniacal liquor and KOH solution adding manganese salt, nickel salt and cobalt salt solution, make the precipitation of the hydroxide of manganese, nickel and cobalt.Washing, behind the 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]
For the performance of the sample that further improves the preparation of NaOH (potassium) and By Ammonia Coprecipitation, the rich lithium solid-solution material oxidant NO that Arunkumar etc. will prepare
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.]
For the performance of the sample that improves the preparation of NaOH (potassium) and By Ammonia Coprecipitation, the rich lithium solid-solution material that the preparation such as Wu coats or mixes.Prepare first the sample that does not coat by coprecipitation, then surperficial by Al by the solution route preparation
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.].
The carbonate coprecipitation method is the carbonate deposition for preparing first nickel, cobalt, manganese, and then mixes with lithium carbonate or lithium hydroxide, through double sintering method or one-stage sintering method or minute one step preparation method, makes lithium-rich anode material.For example, in argon gas atmosphere, Liun etc. are with NH
4HCO
3, (NH
4)
2CO
3Or Na
2CO
3Solution adds NiSO
4, CoSO
4And MnSO
4Mixed solution in, after filtration, after the washing, drying Ni
0.2Co
0.1Mn
0.533(CO
3)
xPredecessor.Predecessor behind 500 ℃ of lower sintering again with Li
2CO
3Mix, obtain spherical powder Li at air atmosphere in 900 ℃ of sintering
1.167Ni
0.2Co
0.1Mn
0.533O
2Can 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, carried out doping vario-property research.For example, Deng etc. is with nickelous sulfate, cobaltous sulfate, manganese sulfate solution and sodium carbonate liquor carbonate synthesis salt precursor (Ni
0.1875Co
0.125Mn
0.6875) CO
3Precursor is suspended in Al (NO
3)
39H
2In the O aqueous solution, drip NH
4F suspension through stirring, after filtering and after 100 ℃ of dryings, at 400 ℃ of lower sintering, prepares 2wt% AlF
3The Li that coats
1.1Ni
0.15Co
0.1Mn
0.55O
1.95This material reaches 304 mAh/g at 55 ℃ reversible capacity, and the coulombic efficiency of circulation reaches 84% first.[Belharouak?Deng?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, carried out step by step preparation research.Shin etc. make Co with cobaltous sulfate, manganese sulfate and ammonium bicarbonate soln reaction
0.5Mn
0.5CO
3Precursor.After this precursor drying and Li
2CO
3Mechanical mixture.In air atmosphere, make 0.5Li respectively at 550 ℃ and 850 ℃ of sintering
2MnO
30.5LiCoO
2Predecessor.This predecessor is mixed with ammonium dihydrogen phosphate, glycolic, nickel nitrate, lithium nitrate, dry in air atmosphere, at 550 ℃ of lower sintering, make 0.5Li again
2MnO
30.5LiNi
0.44Co
0.25Mn
0.31O
2[Shin, C. et al, J. Electrochem. Soc., 2012,159: A121-A127.].
Because when preparing by coprecipitation method, the co-precipitation that no matter forms hydroxide still forms the co-precipitation of carbonate, being prepared all will be through a precipitation, washing precipitation and dry process.This preparation technology's preparation process is many, and preparation process need to be used a large amount of washings, has increased the water pollution.The precipitation solubility product of nickel, manganese, cobalt ions is larger when preparing carbonate deposition by coprecipitation; When preparing precipitation of hydroxide by coprecipitation, not exclusively (the precipitation of hydroxide thing easily and OH for partly precipitated dissolving and the precipitation that causes nickel, manganese, cobalt ions
-Or ammonia forms the solubility that complex compound has increased hydroxide), the stoichiometric proportion of composition that causes the product of final preparation is difficult to accurate control, cause the unstable (chief editor of Wuhan University of chemical property and the heavy-current discharge performance of sample, analytical chemistry (the 2nd edition), Higher Education Publishing House, October nineteen eighty-two, Beijing: the 14th page to the 17th page).Because the heavy-current discharge performance of the rich lithium solid solution cathode material of preparation is all undesirable at present, the present invention attempts further to improve heavy-current discharge performance by add dopant in preparation process.
Summary of the invention
The preparation process of the power consumptions such as the filtration that will experience when coprecipitation prepares, washing, water consumption, in addition, when being prepared by coprecipitation, because hydroxide or the carbonate of manganese ion, cobalt ions, nickel ion can precipitate not exclusively, be difficult to control so that prepare the stoichiometric proportion of product.The problems such as the simple ball milling of common solid sintering technology by product mixes and the technique of sintering preparation exists the reactant mixing inhomogeneous when preparing sample, and the chemical property consistency of product is poor.The present invention can avoid above-mentioned deficiency.For achieving the above object, the technical solution adopted in the present invention is that preparation process is comprised of following steps:
(1) mol ratio according to lithium ion, nickel ion, manganese ion, cobalt ions, M ion is (1.1+0.90x): (1-x) y: (x+z-xz): (1-x) k: (1-x) q takes by weighing respectively the compound of lithium, the compound of nickel, the compound of manganese, compound and the M compound of cobalt.Measure organic monoacid according to following molar ratio relation: (x+z-xz)≤organic monoacid molal quantity≤x+ (1-x) is (z+y+k+q); The span of x, y, z, q, k satisfies following relation simultaneously: 0.25≤x≤0.55,0.05≤y≤0.50,0.2127≤z≤0.55,0.02≤q≤0.15,0.05≤k≤0.30,2y+4z+3k+q-2.9=0.
(2) with the compound of the nickel that takes by weighing, the compound of manganese, compound and the M compound of cobalt, the 1/10 times of wet grinding media to 10 times of volumes that adds total solid capacity, add organic monoacid, wet-milling mixed 3 hours～15 hours, the compound that adds again lithium, the wet-milling mixing obtained predecessor 1 in 3 hours～15 hours.With predecessor 1 usefulness vacuumize or the dry predecessor 2 of spray-dired method preparation.Predecessor 2 is placed air, oxygen rich gas or pure oxygen atmosphere, adopt the preparation of double sintering method or double fragmentation sintering process to consist of xLi
2MnO
3(1-x) Li[Li
0.10Ni
yMn
zCo
kM
q] O
2Rich lithium solid solution cathode material.
Described double fragmentation sintering process is following carries out: predecessor 2 is placed air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, be cooled to room temperature and make the parent Preburning material.After the parent Preburning material pulverized and sieving, again place air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 800 ℃～1050 ℃ of temperature ranges 3 hours～24 hours, prepare rich lithium solid solution cathode material.
Described double sintering method is following carries out: predecessor 2 is placed air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, then place another sintering furnace at air, oxygen rich gas or pure oxygen atmosphere in arbitrary temperature sintering of 800 ℃～1050 ℃ of temperature ranges 3 hours～24 hours, prepare rich lithium solid solution cathode material.
Described weak acid is oxalic acid, amion acetic acid, chloroacetic acid, formic acid or acetic acid.
The compound of described nickel is nickelous carbonate or basic nickel carbonate, or the mixture of the arbitrary proportion of nickelous carbonate and basic nickel carbonate; The compound of described manganese is manganese carbonate or basic carbonate manganese, or the mixture of the arbitrary proportion of manganese carbonate and basic carbonate manganese.The compound of described cobalt is cobalt carbonate, cobalt oxalate or basic cobaltous carbonate, or the mixture of the arbitrary proportion of cobalt carbonate and basic cobaltous carbonate.Described M compound is sodium oxide molybdena, silver oxide, NaOH or potassium hydroxide, or carbonate, chloride, nitrate or the fluoride of sodium, potassium or silver.
Described vacuumize is with the arbitrary temperature of predecessor 1 80 ℃～280 ℃ of temperature ranges, at dry preparation predecessor 2 under the vacuum of 10Pa～10132Pa pressure.Described spray drying is the arbitrary temperature 120 ℃～280 ℃ of temperature ranges, adopts the dry predecessor 2 of spray dryer preparation.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methyl alcohol or formaldehyde; Described oxygen rich gas is the oxygen volume content greater than 21% and less than the gas between 100%.
The equipment of described wet-milling comprises general milling machine, super ball mill or wet milk; The compound of described lithium is lithium carbonate, lithium hydroxide or Lithiagel, or the mixture of its arbitrary proportion.
Compare with the preparation method of other invention, because lithium position, manganese position, nickel position and cobalt position ion are under different preparation conditions in the rich lithium solid solution structure, even only ion mixing phenomenon also usually occurs in preparation technology not simultaneously, has a strong impact on the chemical property of preparation sample.Get clogged in order to prevent that the lithium position is replaced by other valence state ion in the rich lithium solid solution structure, to cause the embedding of lithium ion in the charge and discharge process and deviate from passage, the present invention is doped into monovalent cation in the rich lithium solid solution structure.Lithium position in this spline structure " disappearance " time, the monovalent cation that mixes may preferentially replenish the lithium position that enters rich lithium solid solution structure, prevent the generation of other valence state ion mixing phenomenon, stablize the structure of rich lithium solid solution, improved the cycle performance of preparation sample under the high current charge-discharge condition.
Cost of material of the present invention is lower, and raw material sources are extensive, and preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, has outstanding discharge performance, and the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Description of drawings
Fig. 1 is the sample XRD diffraction pattern of the embodiment of the invention 1 preparation.
Fig. 2 is the discharge curve of sample the 1st circulation under embodiment 1 condition of the embodiment of the invention 1 preparation.
Embodiment
Below in conjunction with embodiment the present invention is further detailed.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
Be 1.325:0.038 according to lithium ion, nickel ion, manganese ion, cobalt ions, sodium ion, formic acid mol ratio: 0.663: 0.145:0.015:0.663 takes by weighing respectively lithium carbonate, nickelous carbonate, manganese carbonate, cobalt carbonate, Na
2O and formic acid.
With nickelous carbonate, manganese carbonate, cobalt carbonate and the Na that takes by weighing
2O mixes, and adds the deionized water of 10 times of volumes of total solid capacity, adds formic acid, mixes 15 hours with the wet-milling of general milling machine, adds lithium carbonate again, and wet-milling mixed 15 hours, prepared predecessor 1; Predecessor 1 is under 80 ℃, dry under the vacuum condition of 10Pa pressure, preparation predecessor 2.Predecessor 2 is placed air atmosphere, and 550 ℃ of lower sintering 15 hours, the chamber of being cooled to made the parent Preburning material; The parent Preburning material is pulverized and crossed 200 mesh sieves, place air atmosphere again, 1050 ℃ of lower sintering 24 hours, preparation consisted of 0.25 Li
2MnO
30.75 Li[Li
0.10Ni
0.05Mn
0.55Co
0.193Na
0.02] O
2Rich lithium solid solution cathode material.The XRD diffraction pattern of preparation sample as shown in Figure 1.The preparation sample is when discharging and recharging under 58 ℃, and at 4.6 to 2.5V voltage ranges, under the 1C electric current, the discharge capacity of the 1st circulation is 190mAh/g, and this sample at this discharge curve that discharges and recharges the 1st circulation under the condition as shown in Figure 2.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Embodiment 2
Mol ratio according to lithium ion, nickel ion, manganese ion, cobalt ions, potassium ion, oxalic acid is 1.595: 0.225: 0.745: 0.0225:0.009:0.992 takes by weighing respectively Lithiagel, basic nickel carbonate, basic carbonate manganese, basic cobaltous carbonate, KOH and oxalic acid.
The basic nickel carbonate, basic carbonate manganese, basic cobaltous carbonate and the KOH that take by weighing are mixed, the ethanol that adds 1/10 times of volume of total solid capacity adds oxalic acid, mixes 3 hours with super ball mill wet-milling, add again Lithiagel, mix obtaining predecessor 1 in 3 hours with super ball mill ball milling; With predecessor 1 predecessor 2 with spray dryer preparation drying under 120 ℃.Predecessor 2 is placed the oxygen-enriched air gas atmosphere of oxygen volume content 22%, and 300 ℃ of lower sintering 3 hours, the sintering furnace that then places another air atmosphere was in 1050 ℃ of lower sintering 3 hours, and preparation consists of 0.55 Li
2MnO
30.45 Li[Li
0.1Ni
0.50Mn
0.4325Co
0.05K
0.02] O
2Rich lithium solid solution cathode material.When the preparation sample discharged and recharged under 58 ℃, at 4.6 to 2.5V voltage ranges, under the 1C electric current, the discharge capacity of the 1st circulation was 220mAh/g.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Embodiment 3
Be 1.415: 0.033: 0.708 according to lithium ion, nickel ion, manganese ion, cobalt ions, silver ion, formic acid mol ratio: 0.0975:0.0975:0.838 takes by weighing respectively lithium hydroxide, nickelous carbonate, manganese carbonate, basic cobaltous carbonate, Ag
2O, formic acid.
With nickelous carbonate, manganese carbonate, basic cobaltous carbonate and the Ag that takes by weighing
2O mixes, and adds the acetone of 10 times of volumes of total solid capacity, adds formic acid, mixes 3 hours with the wet milk wet-milling, adds lithium hydroxide again, mixes obtaining predecessor 1 in 3 hours with the wet milk wet-milling; Under 280 ℃ in the vacuum of 10132Pa pressure dry preparation predecessor 2.Predecessor 2 is placed pure oxygen atmosphere, and 550 ℃ of lower sintering 15 hours, the sintering furnace that then places another pure oxygen atmosphere was in 800 ℃ of lower sintering 24 hours, and preparation consists of 0.35 Li
2MnO
30.65 Li[Li
0.10Ni
0.05Mn
0.55Co
0.15Ag
0.15] O
2Rich lithium solid solution cathode material.When the preparation sample discharged and recharged under 58 ℃, at 4.6 to 2.5V voltage ranges, under the 1C electric current, the discharge capacity of the 1st circulation was 270mAh/g.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Embodiment 4
Be mixture, basic cobaltous carbonate, the Ag of 1.37:0.35:0.4575: the 0.21:0.070:0.46 mixture, basic carbonate manganese and the manganese carbonate weight ratio 1:9 that take by weighing respectively lithium carbonate, basic nickel carbonate and nickelous carbonate weight ratio 1:1 according to lithium ion, nickel ion, manganese ion, cobalt ions, silver ion, oxalic acid mol ratio
2CO
3, oxalic acid.
Mixture, basic cobaltous carbonate and Ag with mixture, basic carbonate manganese and the manganese carbonate weight ratio 1:9 of the basic nickel carbonate that takes by weighing and nickelous carbonate weight ratio 1:1
2CO
3Mix, add the deionized water of 3 times of volumes of total solid capacity, add oxalic acid, wet-milling mixed 10 hours, added lithium carbonate again, mixed obtaining predecessor 1 in 15 hours with wet milk; With the predecessors 2 of predecessor 1 120 ℃ of spray drying preparation dryings.Predecessor 2 is placed air atmosphere, 300 ℃ of sintering 3 hours, be cooled to room temperature and make the parent Preburning material; The parent Preburning material is pulverized and crossed 100 mesh sieves, again place the oxygen-enriched air gas atmosphere of oxygen volume content 50%, 800 ℃ of lower sintering 3 hours, preparation consisted of 0.30 Li
2MnO
30.70 Li[Li
0.10Ni
0.50Mn
0.225Co
0.30Ag
0.10] O
2Rich lithium solid solution cathode material.When the preparation sample discharged and recharged under 58 ℃, at 4.6 to 2.5V voltage ranges, under the 1C electric current, the discharge capacity of the 1st circulation was 279mAh/g.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Embodiment 5
Be 1.325 according to lithium ion, nickel ion, manganese ion, cobalt ions, silver ion, acetic acid mol ratio: 0.038:0.625: 0.195: 0.015:0.856 takes by weighing respectively mixture, the AgNO of lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:9
3, acetic acid.
Mixture, AgNO with the nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and the cobalt carbonate weight ratio 1:9 that take by weighing
3Mix, add the distilled water of 7 times of volumes of total solid capacity, add acetic acid, mixed 11 hours with wet milk, add again lithium hydroxide, mix obtaining predecessor 1 in 12 hours with the general milling machine; Predecessor 1 is prepared dry predecessors 2 at 280 ℃ with spray dryer.Predecessor 2 is placed pure oxygen atmosphere, 300 ℃ of lower sintering 3 hours, be cooled to room temperature and make the parent Preburning material; After the parent Preburning material pulverized and crossing 80 mesh sieves, again place pure oxygen atmosphere, 800 ℃ of lower sintering 3 hours, preparation consisted of 0.25Li
2MnO
30.75 Li[Li
0.10Ni
0.050Mn
0.50Co
0.26Ag
0.02] O
2Rich lithium solid solution cathode material.When the preparation sample discharged and recharged under 58 ℃, at 4.6 to 2.5V voltage ranges, under the 1C electric current, the discharge capacity of the 1st circulation was 289mAh/g.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Embodiment 6
Be 1.37: 0.077: 0.608 according to lithium ion, nickel ion, manganese ion, cobalt ions, silver ion, acetic acid mol ratio: 0.21:0.014: 0.80 takes by weighing respectively mixture, AgF, the acetic acid of lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1.
The nickelous carbonate, basic carbonate manganese, the basic cobaltous carbonate that take by weighing are mixed with mixture, the AgF of cobalt carbonate weight ratio 9:1, the acetone that adds 6 times of volumes of total solid capacity adds acetic acid, and wet-milling mixed 15 hours, add lithium hydroxide, the wet-milling mixing obtained predecessor 1 in 3 hours again.Predecessor 1 is prepared dry predecessors 2 at 200 ℃ with spray dryer.Predecessor 2 is placed the oxygen-enriched air atmosphere of oxygen volume content 99%, 350 ℃ of lower sintering 24 hours, be cooled to room temperature and make the parent Preburning material; After the parent Preburning material pulverized and crossing 80 mesh sieves, then place the oxygen-enriched air gas atmosphere of oxygen volume content 59%, 980 ℃ of sintering 20 hours, preparation consisted of 0.30 Li
2MnO
30.70 Li[Li
0.10Ni
0.11Mn
0.44Co
0.30Ag
0.02] O
2Rich lithium solid solution cathode material.When the preparation sample discharged and recharged under 58 ℃, at 4.6 to 2.5V voltage ranges, under the 1C electric current, the discharge capacity of the 1st circulation was 170mAh/g.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Embodiment 7
Be 1.37: 0.077: 0.608 according to lithium ion, nickel ion, manganese ion, cobalt ions, silver ion, acetic acid mol ratio: 0.21:0.014: 0.90 takes by weighing respectively mixture, AgF, the acetic acid of lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:9.
The nickelous carbonate, basic carbonate manganese, the basic cobaltous carbonate that take by weighing are mixed with mixture, the AgF of cobalt carbonate weight ratio 1:9, the acetone that adds 6 times of volumes of total solid capacity adds acetic acid, and wet-milling mixed 15 hours, add lithium hydroxide, the wet-milling mixing obtained predecessor 1 in 3 hours again.Predecessor 1 at 200 ℃ of heat dryings under normal pressure, is prepared dry predecessor 2.Predecessor 2 is placed air atmosphere, 350 ℃ of lower sintering 24 hours, be cooled to room temperature and make the parent Preburning material; After the pulverizing of parent Preburning material and crossing 80 mesh sieves, place the oxygen-enriched air gas atmosphere of oxygen volume content 51%, 980 ℃ of sintering 20 hours, preparation consisted of 0.30 Li2MnO30.70 Li[Li0.10Ni0.11Mn0.44Co0.30Ag0.02] the rich lithium solid solution cathode material of O2.When the preparation sample discharged and recharged under 55 ℃, at 4.6 to 2.5V voltage ranges, under the 1C electric current, the discharge capacity of the 1st circulation was 182mAh/g.
Compare with other inventive method, cost of material of the present invention is lower, and raw material sources are extensive, preparation process is simple, and is consuming time few, and the electrode material of preparation forms evenly, have outstanding discharge performance, the cycle performance that particularly discharges under large current condition is good, for industrialization is laid a good foundation.
Claims (10)
1. be partly dissolved the method for the rich lithium solid solution cathode material of the standby doping monovalent ion of legal system, it is characterized in that preparation process is comprised of following steps:
(1) mol ratio according to lithium ion, nickel ion, manganese ion, cobalt ions, M ion is (1.1+0.90x): (1-x) y: (x+z-xz): (1-x) k: (1-x) q takes by weighing respectively the compound of lithium, the compound of nickel, the compound of manganese, compound and the M compound of cobalt; Measure organic monoacid according to following molar ratio relation: (x+z-xz)≤organic monoacid molal quantity≤x+ (1-x) is (z+y+k+q); The span of x, y, z, q, k satisfies following relation simultaneously: 0.25≤x≤0.55,0.05≤y≤0.50,0.2127≤z≤0.55,0.02≤q≤0.15,0.05≤k≤0.30,2y+4z+3k+q-2.9=0;
(2) with the compound of the nickel that takes by weighing, the compound of manganese, compound and the M compound of cobalt, the 1/10 times of wet grinding media to 10 times of volumes that adds total solid capacity, add organic monoacid, wet-milling mixed 3 hours～15 hours, the compound that adds again lithium, the wet-milling mixing obtained predecessor 1 in 3 hours～15 hours; With predecessor 1 usefulness vacuumize or the dry predecessor 2 of spray-dired method preparation; Predecessor 2 is placed air, oxygen rich gas or pure oxygen atmosphere, adopt the preparation of double sintering method or double fragmentation sintering process to consist of xLi
2MnO
3(1-x) Li[Li
0.10Ni
yMn
zCo
kM
q] O
2Rich lithium solid solution cathode material;
Described double fragmentation sintering process is following carries out: predecessor 2 is placed air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, be cooled to room temperature and make the parent Preburning material; After the parent Preburning material pulverized and sieving, again place air, oxygen rich gas or pure oxygen, arbitrary temperature sintering of 800 ℃～1050 ℃ of temperature ranges 3 hours～24 hours, prepare rich lithium solid solution cathode material;
Described double sintering method is following carries out: predecessor 2 is placed air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, then place another sintering furnace at air, oxygen rich gas or pure oxygen atmosphere in arbitrary temperature sintering of 800 ℃～1050 ℃ of temperature ranges 3 hours～24 hours, prepare rich lithium solid solution cathode material.
2. the method that is partly dissolved the rich lithium solid solution cathode material of the standby doping monovalent ion of legal system according to claim 1 is characterized in that described weak acid is oxalic acid, amion acetic acid, chloroacetic acid, formic acid or acetic acid.
3. the legal system that is partly dissolved according to claim 1 is for the method for the rich lithium solid solution cathode material of doping monovalent ion, the compound that it is characterized in that described nickel is nickelous carbonate or basic nickel carbonate, or the mixture of the arbitrary proportion of nickelous carbonate and basic nickel carbonate.
4. the legal system that is partly dissolved according to claim 1 is for the method for the rich lithium solid solution cathode material of doping monovalent ion, the compound that it is characterized in that described manganese is manganese carbonate or basic carbonate manganese, or the mixture of the arbitrary proportion of manganese carbonate and basic carbonate manganese.
5. the legal system that is partly dissolved according to claim 1 is for the method for the rich lithium solid solution cathode material of doping monovalent ion, the compound that it is characterized in that described cobalt is cobalt carbonate, cobalt oxalate or basic cobaltous carbonate, or the mixture of the arbitrary proportion of cobalt carbonate and basic cobaltous carbonate.
6. the legal system that is partly dissolved according to claim 1 is for the method for the rich lithium solid solution cathode material of doping monovalent ion, it is characterized in that described M compound is sodium oxide molybdena, silver oxide, NaOH or potassium hydroxide, or carbonate, chloride, nitrate or the fluoride of sodium, potassium or silver.
7. the legal system that is partly dissolved according to claim 1 is for the method for the rich lithium solid solution cathode material of doping monovalent ion, it is characterized in that described vacuumize is with the arbitrary temperature of predecessor 1 80 ℃～280 ℃ of temperature ranges, at dry preparation predecessor 2 under the vacuum of 10Pa～10132Pa pressure.
8. the legal system that is partly dissolved according to claim 1 is for the method for the rich lithium solid solution cathode material of doping monovalent ion, it is characterized in that described spray drying is the arbitrary temperature 120 ℃～280 ℃ of temperature ranges, adopt the dry predecessor 2 of spray dryer preparation.
9. the method that is partly dissolved the rich lithium solid solution cathode material of the standby doping monovalent ion of legal system according to claim 1 is characterized in that described wet grinding media is deionized water, distilled water, ethanol, acetone, methyl alcohol or formaldehyde; Described oxygen rich gas is the oxygen volume content greater than 21% and less than the gas between 100%.
10. the method that is partly dissolved the rich lithium solid solution cathode material of the standby doping monovalent ion of legal system according to claim 1 is characterized in that the equipment of described wet-milling comprises general milling machine, super ball mill or wet milk; The compound of described lithium is lithium carbonate, lithium hydroxide or Lithiagel, or the mixture of its arbitrary proportion.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103606668A (en) * | 2013-11-28 | 2014-02-26 | 福建师范大学 | Preparation method of monovalent ion-doped spinel rich-lithium lithium manganate anode material |
| CN103746105A (en) * | 2013-11-28 | 2014-04-23 | 福建师范大学 | Method for preparing spinel type lithium-rich lithium manganate cathode material by doping molybdenum ions |
| CN107180959A (en) * | 2017-06-07 | 2017-09-19 | 北京当升材料科技股份有限公司 | It is a kind of to mix rich lithium manganese base solid solution positive electrode of sodium and preparation method thereof |
| CN109786736A (en) * | 2018-12-28 | 2019-05-21 | 中南大学 | A kind of nickel cobalt rubidium manganate lithium material and its preparation method and application |
| CN109802111A (en) * | 2018-12-28 | 2019-05-24 | 中南大学 | A kind of nickelic tertiary cathode material of rubidium element doping and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090155691A1 (en) * | 2007-12-13 | 2009-06-18 | Uchicago Argonne, Llc | Positive electrode for a lithium battery |
| CN102664253A (en) * | 2012-05-09 | 2012-09-12 | 奇瑞汽车股份有限公司 | Lithium-rich material and preparation method thereof and lithium ion battery containing same |
-
2012
- 2012-10-15 CN CN201210391688.1A patent/CN102881880B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090155691A1 (en) * | 2007-12-13 | 2009-06-18 | Uchicago Argonne, Llc | Positive electrode for a lithium battery |
| CN102664253A (en) * | 2012-05-09 | 2012-09-12 | 奇瑞汽车股份有限公司 | Lithium-rich material and preparation method thereof and lithium ion battery containing same |
Non-Patent Citations (2)
| Title |
|---|
| 任岩等: "(1-x)Li2MnO3•xLiNi1/2Mn1/2O2的低温固相制备及电化学性能研究", 《华南师范大学学报（自然科学版）》 * |
| 任岩等: "(1-x)Li2MnO3•xLiNi1/2Mn1/2O2的低温固相制备及电化学性能研究", 《华南师范大学学报（自然科学版）》, 30 November 2009 (2009-11-30) * |
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| CN103606668A (en) * | 2013-11-28 | 2014-02-26 | 福建师范大学 | Preparation method of monovalent ion-doped spinel rich-lithium lithium manganate anode material |
| CN103746105A (en) * | 2013-11-28 | 2014-04-23 | 福建师范大学 | Method for preparing spinel type lithium-rich lithium manganate cathode material by doping molybdenum ions |
| CN103746105B (en) * | 2013-11-28 | 2015-11-11 | 福建师范大学 | The method of spinel type lithium-rich lithium manganate cathode material is prepared by doping molybdenum ion |
| CN103606668B (en) * | 2013-11-28 | 2016-04-13 | 福建师范大学 | The preparation method of the spinel lithium-rich lithium manganate cathode material of doping monovalent ion |
| CN107180959A (en) * | 2017-06-07 | 2017-09-19 | 北京当升材料科技股份有限公司 | It is a kind of to mix rich lithium manganese base solid solution positive electrode of sodium and preparation method thereof |
| CN107180959B (en) * | 2017-06-07 | 2020-01-17 | 北京当升材料科技股份有限公司 | Sodium-doped lithium-rich manganese-based solid solution cathode material and preparation method thereof |
| CN109786736A (en) * | 2018-12-28 | 2019-05-21 | 中南大学 | A kind of nickel cobalt rubidium manganate lithium material and its preparation method and application |
| CN109802111A (en) * | 2018-12-28 | 2019-05-24 | 中南大学 | A kind of nickelic tertiary cathode material of rubidium element doping and its preparation method and application |
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