CN102881891B - Method for preparing trivalent ion-doped lithium-rich solid solution cathode material - Google Patents

Method for preparing trivalent ion-doped lithium-rich solid solution cathode material Download PDF

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CN102881891B
CN102881891B CN201210391471.0A CN201210391471A CN102881891B CN 102881891 B CN102881891 B CN 102881891B CN 201210391471 A CN201210391471 A CN 201210391471A CN 102881891 B CN102881891 B CN 102881891B
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carbonate
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solid solution
cathode material
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CN102881891A (en
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童庆松
肖斌
蔡斌
周惠
黄娟
姜祥祥
韩铭
潘樱
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Fujian Normal University
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Abstract

The invention relates to a method for preparing trivalent ion-doped lithium-rich solid solution cathode material, which comprises the steps of: respectively weighing compounds of lithium, nickel, manganese and cobalt as well as compound M according to the molar ratio of (1.1+ 0.90* x):(1-x)* y:(1+z-x*z):(1-x)* k:(1-x)* q among lithium ionic, nickel ionic, manganese ionic, cobalt ionic and M ionic; mixing the weighed compounds of nickel, manganese and cobalt with the compound M; adding wet grinding medium and organic weak acid into the mixture; performing wet grinding, mixing and adding the compound of lithium; performing wet grinding and mixing; drying by a vacuum drying method or spray drying method; putting the product in the air, oxygen-rich gas or pure-oxygen gas; and finally, adopting a two-stage sintering method or two times of multi-step sintering method to prepare the lithium-rich solid solution cathode material. The prepared electrode material is uniform in composition, has excellent discharge property, and has better discharge cycle performance especially under the condition of large current.

Description

The preparation method of the rich lithium solid solution cathode material of doping trivalent ion
Technical field
The invention belongs to technical field prepared by battery electrode material, be specifically related to a kind of preparation method that 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 features such as operating voltage is high, cheap, environmental friendliness, but the reversible capacity of this positive electrode is lower, a capacity of putting when 1C rate charge-discharge only has 90-100mAh/g; At high temperature the discharge capacity of this positive electrode can carry out rapid decay along with 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 is high, Heat stability is good, cycle performance are good, thus attract the high interest of domestic and international experts and scholars.The current method preparing rich lithium solid solution cathode material employing comprises coprecipitation method, sol gel process, solid-phase sintering method etc.In this several preparation method, in order to improve the chemical property preparing sample further, as improved the current efficiency of the 1st circulation, improving the discharge performance etc. of different multiplying electric current, also having the research report of some doping preparation method.
In co-precipitation preparation method, the difference according to the precipitation generated is divided into again hydroxide coprecipitation step and carbonate co-precipitation.
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, discuss respectively below:
Lithium hydroxide coprecipitation method adopts LiOH to be precipitation reagent, added by LiOH solution in the solution of manganese salt, nickel salt and cobalt salt, the compound of the precipitation of hydroxide of obtained manganese, nickel and cobalt.The compound of precipitation of hydroxide is washed, after drying, mixes with excessive LiOH, obtain rich lithium lithium manganate material [Guo X.et al.J.Power Sources, 2008,184:414 – 419. through one section or two sections or two-step 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 lithium hydroxide coprecipitation method is prepared by Wu Xiaobiao etc. 0.2mn 0.54ni 0.13co 0.13] O 2carry out carbon coated process; Shi etc. are by the Li of preparation 1.048mn 0.381ni 0.286co 0.286o 2carry out magnetron sputtering process, the positive electrode of preparation carbon coated.Result shows, carbon encapsulated material has high-rate discharge ability (5C, 145mAh/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 lithium solid-solution material acid or acid salt process, with improving SNR [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 process has higher capacity and good multiplying power discharging property.
In order to improve the multiplying power discharging property of sample prepared by lithium hydroxide coprecipitation method further, Rodrigues etc. add urea in the preparation, utilize urea decomposition product to promote the generation of co-precipitation further.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, determines ureaclastic optimum temperature by hydro thermal method, microwave attenuation materials method or 100 DEG C of heatings.Research shows, along with the increase of reacting solution pH value, sediment is separated out from solution.In air atmosphere after drying, the LiOH of the hydroxide of drying and excessive 3% is synthesized LiNi xmn xco (1 – 2x)o 2predecessor.After predecessor granulation, respectively at 500 DEG C and 900 DEG C of sintering in air atmosphere, last quench cooled.
NaOH (potassium) and ammoniacal liquor coprecipitation method adopt the mixed solution of ammoniacal liquor and NaOH or KOH solution as precipitation reagent, ammoniacal liquor and NaOH solution or ammoniacal liquor and KOH solution are added in manganese salt, nickel salt and cobalt salt solution, the precipitation of the hydroxide of obtained manganese, nickel and cobalt.After washing, dry hydrogen oxide precipitation, with stoichiometry little over LiOH or Li measured 2cO 3mixing, obtains 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 to improve the performance of sample prepared by NaOH (potassium) and By Ammonia Coprecipitation further, 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, Wu etc. prepare rich lithium solid-solution material that is coated or doping.Not coated sample is first prepared by coprecipitation, then surperficial by Al by solution route preparation 2o 3, CeO 2, ZrO 2, SiO 2, ZnO, AlPO 4with rich lithium solid-solution material (1-z) Li [Li of F-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 co-precipitation is the carbonate deposition first preparing 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, and obtained lithium-rich anode material.Such as, 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 drying Ni 0.2co 0.1mn 0.533(CO 3) xpredecessor.Predecessor after sintering at 500 DEG C again with Li 2cO 3mixing, obtains spherical powder Li at air atmosphere in 900 DEG C of sintering 1.167ni 0.2co 0.1mn 0.533o 2.340mAh/g can be reached in 2.0 – 4.8V 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 to improve coulombic efficiency and the discharge performance of sample prepared by carbonate co-precipitation further, carry out doping vario-property research.Such as, Deng etc. are 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 Al (NO 3) 39H 2in the O aqueous solution, drip NH 4f suspension, through stirring, after filtering and after 100 DEG C of dryings, sintering, preparing 2wt%AlF at 400 DEG C 3coated Li 1.1ni 0.15co 0.1mn 0.55o 1.95.This material reaches 304mAh/g at the reversible capacity of 55 DEG C, and the coulombic efficiency circulated first reaches 84%.[Belharouak?Deng?H.et?al,J.Electrochem.Soc.,2010，157：A1035-A1039.]
In order to improve the discharge performance of sample prepared by carbonate co-precipitation further, carry out preparation research step by step.Cobaltous sulfate, manganese sulfate and ammonium bicarbonate soln react by Shin etc., obtained Co 0.5mn 0.5cO 3precursor.After this precursor drying and Li 2cO 3mechanical mixture.In air atmosphere, respectively at 550 DEG C and 850 DEG C of obtained 0.5Li of sintering 2mnO 30.5LiCoO 2predecessor.This predecessor is mixed with ammonium dihydrogen phosphate, glycolic, nickel nitrate, lithium nitrate, dry in air atmosphere, then sinter at 550 DEG C, obtained 0.5Li 2mnO 30.5LiNi 0.44co 0.25mn 0.31o 2[Shin, C.et al, J.Electrochem.Soc., 2012,159:A121-A127.].
During owing to being prepared by coprecipitation method, no matter form the co-precipitation of hydroxide or form the co-precipitation of carbonate, being prepared all will through the process of a precipitation, washing precipitation and drying.This preparation technology's preparation process is many, and preparation process needs to use a large amount of washings, adds water pollutions.When preparing carbonate deposition by coprecipitation, the precipitation solubility product of nickel, manganese, cobalt ions is larger; When preparing precipitation of hydroxide by coprecipitation, not exclusively (precipitation of hydroxide thing easily and OH for the precipitation that partly precipitated dissolves and causes nickel, manganese, cobalt ions -or ammonia forms the solubility that complex compound increases hydroxide), the stoichiometric proportion of the composition of the product of final preparation is caused to be difficult to accurate control, cause the chemical property of sample and instability (the Wuhan University chief editor of heavy-current discharge performance, 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 prepared at present is all undesirable, the present invention attempts to improve heavy-current discharge performance further by adding dopant in preparation process.
In sum, the preparation process of the power consumptions such as filtration, washing, water consumption will be experienced time prepared by coprecipitation, in addition, when being prepared by coprecipitation, because the hydroxide of manganese ion, cobalt ions, nickel ion or carbonate can precipitate not exclusively, the stoichiometric proportion preparing product is made to be difficult to control.Common solid sintering technology by the mixing of product simple ball milling, then the technique carrying out sintering preparation to there is reactant mixing uneven, the problems such as the chemical property consistency difference of product.
Summary of the invention
For avoiding the deficiencies in the prior art, the technical solution adopted in the present invention is:
(1) being (1.1+0.90x) according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions, M ion: (1-x) y:(x+z-xz): (1-x) k:(1-x) q takes the compound of the compound of lithium, the compound of nickel, the compound of manganese, the compound of cobalt and M respectively; Organic monoacid is got: (x+z-xz)≤organic monoacid molal quantity≤x+ (1-x) (z+y+k+q) according to following mole of span; The span of x, y, z, q, k meets following relation simultaneously: 0.25≤x≤0.60,0.05≤y≤0.55,0.1≤z≤0.5,0.02≤q≤0.15,0.05≤k≤0.30,2y+4z+3k+3q-2.9=0.
(2) by the compound of the compound of the nickel that takes, the compound of manganese, the compound of cobalt and M, add 1/10 times of wet grinding media to 10 times of volumes of total solid capacity, add organic monoacid, wet-milling mixes 3 hours ~ 15 hours, add the compound of lithium again, wet-milling mixes 3 hours ~ 15 hours and obtains predecessor 1; Predecessor 1 vacuumize or spray-dired method are prepared dry predecessor 2; Predecessor 2 is placed in air, oxygen rich gas or pure oxygen atmosphere, adopts double sintering method or double fragmentation sintering process to prepare theory and consist of xLi 2mnO 3(1-x) Li [Li 0.1ni ymn zco km q] O 2rich lithium solid solution cathode material.Described M is Sc, Cr or Al.
Described double fragmentation sintering process is carried out as follows: predecessor 2 is placed in air, oxygen rich gas or pure oxygen atmosphere, sinters 3 hours ~ 15 hours in arbitrary temperature of 300 DEG C ~ 550 DEG C of temperature ranges, is cooled to room temperature and obtains parent Preburning material; Parent Preburning material is pulverized and after sieving, is placed in air, oxygen rich gas or pure oxygen atmosphere, sinters 3 hours ~ 24 hours in arbitrary temperature of 800 DEG C ~ 1050 DEG C of temperature ranges, prepare rich lithium solid solution cathode material.
Described double sintering method is carried out as follows: predecessor 2 is placed in air, oxygen rich gas or pure oxygen atmosphere, 3 hours ~ 15 hours are sintered in arbitrary temperature of 300 DEG C ~ 550 DEG C of temperature ranges, then be placed in another sintering furnace and sinter 3 hours ~ 24 hours at air, oxygen rich gas or pure oxygen atmosphere in arbitrary temperature of 800 DEG C ~ 1050 DEG C of temperature ranges, 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.The compound of described M is Sc 2o 3, Sc 2(CO 3) 3, Sc (NO 3) 3, Sc (OH) 3, Cr 2o 3, Cr (OH) 3, Cr (NO 3) 3, Al (NO 3) 3, Al 2o 3or Al (OH) 3.
Described vacuumize is by the arbitrary temperature of predecessor 1 80 DEG C ~ 280 DEG C of temperature ranges, dry at the arbitrary vacuum under pressure between 10Pa ~ 10132Pa pressure limit, prepares predecessor 2.Described spraying dry is the arbitrary temperature 110 DEG C ~ 280 DEG C of temperature ranges, adopts the predecessor 2 that spray dryer preparation is dry.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methyl alcohol or formaldehyde.Described oxygen rich gas is that oxygen volume content is greater than 21% and is less than the gas between 100%.
Described wet-milling mixing, general milling machine, super ball mill or wet milk carry out.The compound of described lithium is lithium carbonate, lithium hydroxide or Lithiagel, or the mixture of its arbitrary proportion.
Compared with other inventive method, the present invention selects cation valence to be that the compound of the M of trivalent is as dopant, the strong electrostatic attraction of Tricationic to anion is utilized to stablize the structure of the rich lithium solid solution cathode material of preparation, select original manganese ion in the ionic radius of Tricationic for adulterating and rich lithium solid solution cathode material, the ionic radius of nickel ion or cobalt ions is close, the Tricationic of such doping easily embeds in the structure of the rich lithium solid solution cathode material of preparation and can not damage the original structure of rich lithium solid solution cathode material.
Cost of material of the present invention is lower, and raw material sources are extensive, and preparation process is simple, consuming time few, and evenly, have outstanding discharge performance, the cycle performance particularly discharged under conditions of high current is good, for industrialization is laid a good foundation for the electrode material composition of preparation.
Accompanying drawing explanation
Fig. 1 is sample XRD diffraction pattern prepared by the embodiment of the present invention 2.
Fig. 2 is the charging and discharging curve that sample the 1st circulates.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed.Embodiment is only supplement further of the present invention and illustrate, instead of the restriction to invention.
Embodiment 1
Be that 1.325:0.413:0.475:0.135:0.015:0.475 takes lithium carbonate, nickelous carbonate, manganese carbonate, cobalt carbonate, Sc respectively according to lithium ion, nickel ion, manganese ion, cobalt ions, scandium ion, formic acid mol ratio 2o 3and formic acid.
By the nickelous carbonate, manganese carbonate, cobalt carbonate and the Sc that take 2o 3mixing, add the deionized water of 10 times of volumes of total solid capacity, add formic acid, mix 15 hours, then add lithium carbonate with the wet-milling of general milling machine, wet-milling mixes 15 hours and obtains predecessor 1; Predecessor 1 is at 800 DEG C, and under the vacuum condition of 10132Pa pressure, predecessor 2 is prepared in drying.Predecessor 2 is placed in air atmosphere, at 550 DEG C, sinters 15 hours, be cooled to room temperature and obtain parent Preburning material; By the pulverizing of parent Preburning material and after crossing 200 mesh sieves, be again placed in air atmosphere, at 1050 DEG C, keep temperature to sinter 24 hours, preparation consists of 0.25Li 2mnO 30.75Li [Li 0.1ni 0.55mn 0.30co 0.18sc 0.02] O 2rich lithium solid solution cathode material.Prepare sample at 45 DEG C during discharge and recharge, at 4.6 to 2.5V voltage range, under 1.3C electric current, the discharge capacity of the 1st circulation is 147mAh/g.As shown in Figure 1, the charging and discharging curve that sample the 1st circulates as shown in Figure 2 for the XRD diffraction pattern of sample.
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 discharged under conditions of high current is good, for industrialization is laid a good foundation.
Embodiment 2
Be that 1.64:0.02:0.80:0.0467:0.06:0.93 takes Lithiagel, basic nickel carbonate, basic carbonate manganese, basic cobaltous carbonate, Al respectively according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions, aluminium ion, oxalic acid 2o 3and oxalic acid.
By the basic nickel carbonate, basic carbonate manganese, basic cobaltous carbonate, the Al that take 2o 3mixing, adds the ethanol of 1/10 times of volume of total solid capacity, adds oxalic acid, mix 3 hours, then add Lithiagel with super ball mill wet-milling, mix 3 hours obtain predecessor 1 with super ball mill; Predecessor 1 is prepared dry predecessor 2 with spray dryer at 110 DEG C.Predecessor 2 is placed in the oxygen-enriched air gas atmosphere of oxygen volume content 22%, sinters 3 hours, be then placed in another sintering furnace and at 1050 DEG C, sinter 3 hours at air atmosphere at 300 DEG C, preparation consists of 0.60Li 2mnO 30.40Li [Li 0.1ni 0.05mn 0.50co 0.117al 0.15] O 2rich lithium solid solution cathode material.Prepare sample at 45 DEG C during discharge and recharge, at 4.6 to 2.5V voltage range, under 0.8C electric current, the discharge capacity of the 1st circulation is 175mAh/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 discharged under conditions of high current is good, for industrialization is laid a good foundation.
Embodiment 3
Be that 1.55:0.175:0.70:0.025:0.075:0.975 takes lithium hydroxide, nickelous carbonate, manganese carbonate, basic cobaltous carbonate, Al (OH) respectively according to lithium ion, nickel ion, manganese ion, cobalt ions, aluminium ion, acetic acid mol ratio 3, acetic acid.
By the nickelous carbonate, manganese carbonate, basic cobaltous carbonate and the Al (OH) that take 3mixing, adds the acetone of 8 times of volumes of total solid capacity, adds acetic acid, mix 15 hours, then add lithium hydroxide with wet milk wet-milling, mix 15 hours obtain predecessor 1 with wet milk wet-milling; At 80 DEG C, under the vacuum of 10132Pa pressure, predecessor 2 is prepared in drying.Predecessor 2 is placed in pure oxygen atmosphere, sinters 15 hours, be then placed in another sintering furnace and at 800 DEG C, sinter 24 hours at pure oxygen atmosphere at 550 DEG C, preparation consists of 0.50Li 2mnO 30.50Li [Li 0.1ni 0.35mn 0.40co 0.05al 0.15] O 2rich lithium solid solution cathode material.
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 discharged under conditions of high current is good, for industrialization is laid a good foundation.
Embodiment 4
Be mixture, basic cobaltous carbonate, the Cr that 1.37:0.245:0.449:0.210:0.105:0.60 takes the mixture of lithium carbonate, basic nickel carbonate and nickelous carbonate weight ratio 1:1, basic carbonate manganese and manganese carbonate weight ratio 1:9 respectively according to lithium ion, nickel ion, manganese ion, cobalt ions, chromium ion, oxalic acid mol ratio 2o 3, oxalic acid.
By mixture, basic cobaltous carbonate, the Cr of the mixture of the basic nickel carbonate that takes and nickelous carbonate weight ratio 1:1, basic carbonate manganese and manganese carbonate weight ratio 1:9 2o 3, add the ethanol of 3 times of volumes of total solid capacity, add acetic acid, mix 15 hours with the wet-milling of general milling machine, then add lithium carbonate, mix 15 hours with wet milk and obtain predecessor 1; Predecessor 1 is prepared dry predecessor 2 at 280 DEG C with spray dryer.Predecessor 2 is placed in air atmosphere, sinters 3 hours at 300 DEG C, be cooled to room temperature and obtain parent Preburning material; By the pulverizing of parent Preburning material and after crossing 50 mesh sieves, be again placed in air atmosphere, at 800 DEG C, sinter 3 hours, preparation consists of 0.30Li 2mnO 30.70Li [Li 0.1ni 0.35mn 0.213co 0.30cr 0.15] O 2rich lithium solid solution cathode material.
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 discharged under conditions of high current is good, for industrialization is laid a good foundation.
Embodiment 5
According to lithium ion, nickel ion, manganese ion, cobalt ions, Cr (OH) 3, chloroacetic acid mol ratio is mixture, the Cr (OH) that 1.46:0.21:0.58:0.14:0.06:0.70 takes lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:9 respectively 3, chloroacetic acid.
By the mixture of nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:9 that takes and Cr (OH) 3mixing, adds the distilled water of 7 times of volumes of total solid capacity, adds amion acetic acid, mix 11 hours, then add lithium hydroxide with wet milk, mix 12 hours obtained predecessors 1 with general milling machine ball milling; By the predecessor 2 of predecessor 1 165 DEG C of spraying dry preparation dryings.Predecessor 2 is placed in pure oxygen atmosphere, at 550 DEG C, sinters 3 hours, be cooled to room temperature and obtain parent Preburning material; By the pulverizing of parent Preburning material and after crossing 100 mesh sieves, be again placed in pure oxygen atmosphere, at 800 DEG C, sinter 24 hours, preparation consists of 0.40Li 2mnO 30.60Li [Li 0.1ni 0.35mn 0.30co 0.233cr 0.10] O 2rich lithium solid solution cathode material.Prepare sample at 45 DEG C during discharge and recharge, at 4.6 to 2.5V voltage range, under 0.8C electric current, the discharge capacity of the 1st circulation is 115mAh/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 discharged under conditions of high current is good, for industrialization is laid a good foundation.
Embodiment 6
Be mixture, the Al (OH) that 1.46:0.198:0.58:0.178:0.03:0.80 takes lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1 respectively according to lithium ion, nickel ion, manganese ion, cobalt ions, aluminium ion, formic acid mol ratio 3, formic acid.
By mixture, the Al (OH) of nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1 that take 3mixing, add the distilled water of 6 times of volumes of total solid capacity, add formic acid, wet-milling mixes 15 hours, then adds lithium hydroxide, and wet-milling mixes 3 hours and obtains predecessor 1; 280 DEG C in the vacuum of 10Pa pressure drying prepare predecessor 2.Predecessor 2 is placed in the oxygen-enriched air gas atmosphere of oxygen volume content 99%, sinters 15 hours at 550 DEG C, be then placed in another sintering furnace and sinter 3 hours at the oxygen-enriched air gas atmosphere of oxygen volume content 99% in 800 DEG C, preparation consists of 0.40Li 2mnO 30.60Li [Li 0.1ni 0.33mn 0.30co 0.297al 0.05] O 2rich lithium solid solution cathode material.
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 discharged under conditions of high current is good, for industrialization is laid a good foundation.
Embodiment 7
Be mixture, the Al (OH) that 1.46:0.198:0.58:0.178:0.03:0.60 takes lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:1 respectively according to lithium ion, nickel ion, manganese ion, cobalt ions, aluminium ion, formic acid mol ratio 3, formic acid.
By mixture, the Al (OH) of nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:1 that take 3mixing, add the distilled water of 6 times of volumes of total solid capacity, add formic acid, wet-milling mixes 15 hours, then adds lithium hydroxide, and wet-milling mixes 3 hours and obtains predecessor 1; 250 DEG C in the vacuum of 100Pa pressure drying prepare predecessor 2.Predecessor 2 is placed in the oxygen-enriched air gas atmosphere of oxygen volume content 90%, sinters 10 hours at 500 DEG C, be then placed in another sintering furnace and sinter 5 hours at the oxygen-enriched air gas atmosphere of oxygen volume content 30% in 850 DEG C, preparation consists of 0.40Li 2mnO 30.60Li [Li 0.1ni 0.33mn 0.30co 0.297al 0.05] O 2rich lithium solid solution cathode material.
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 discharged under conditions of high current is good, for industrialization is laid a good foundation.
Embodiment 8
Be mixture, the Al (OH) that 1.46:0.198:0.58:0.178:0.03:0.90 takes lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:2 respectively according to lithium ion, nickel ion, manganese ion, cobalt ions, aluminium ion, formic acid mol ratio 3, formic acid.
By mixture, the Al (OH) of nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1 that take 3mixing, add the distilled water of 10 times of volumes of total solid capacity, add formic acid, wet-milling mixes 10 hours, then adds lithium hydroxide, and wet-milling mixes 5 hours and obtains predecessor 1; Prepare drying at 230 DEG C with spraying dry agent and prepare predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere, sinters 15 hours at 500 DEG C, be then placed in another sintering furnace and sinter 5 hours at the oxygen-enriched air gas atmosphere of oxygen volume content 50% in 900 DEG C, preparation consists of 0.40Li 2mnO 30.60Li [Li 0.1ni 0.33mn 0.30co 0.297al 0.05] O 2rich lithium solid solution cathode material.
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 discharged under conditions of high current is good, for industrialization is laid a good foundation.

Claims (10)

1. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion, is characterized in that preparation process is made up of following steps:
(1) be (1.1+0.90x) according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions, M ion: the compound of the compound of (1-x) y: (x+z-xz): (1-x) k: (1-x) q compound taking lithium respectively, nickel, the compound of manganese, the compound of cobalt and M; Organic monoacid is got: (x+z-xz)≤organic monoacid molal quantity≤x+ (1-x) (z+y+k+q) according to following mole of span; The span of x, y, z, q, k meets following relation simultaneously: 0.25≤x≤0.60,0.05≤y≤0.55,0.1≤z≤0.5,0.02≤q≤0.15,0.05≤k≤0.30,2y+4z+3k+3q-2.9=0; Described M is Sc, Cr or Al;
(2) by the compound of the compound of the nickel that takes, the compound of manganese, the compound of cobalt and M, add 1/10 times of wet grinding media to 10 times of volumes of total solid capacity, add organic monoacid, wet-milling mixes 3 hours ~ 15 hours, add the compound of lithium again, wet-milling mixes 3 hours ~ 15 hours and obtains predecessor 1; Predecessor 1 vacuumize or spray-dired method are prepared dry predecessor 2; Predecessor 2 is placed in air, oxygen rich gas or pure oxygen atmosphere, adopts double sintering method or the preparation of 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 carried out as follows: predecessor 2 is placed in air, oxygen rich gas or pure oxygen atmosphere, sinters 3 hours ~ 15 hours in arbitrary temperature of 300 DEG C ~ 550 DEG C of temperature ranges, is cooled to room temperature and obtains parent Preburning material; Parent Preburning material is pulverized and after sieving, is placed in air, oxygen rich gas or pure oxygen atmosphere, sinters 3 hours ~ 24 hours in arbitrary temperature of 800 DEG C ~ 1050 DEG C of temperature ranges, prepare rich lithium solid solution cathode material;
Described double sintering method is carried out as follows: predecessor 2 is placed in air, oxygen rich gas or pure oxygen atmosphere, 3 hours ~ 15 hours are sintered in arbitrary temperature of 300 DEG C ~ 550 DEG C of temperature ranges, then be placed in another sintering furnace and sinter 3 hours ~ 24 hours at air, oxygen rich gas or pure oxygen atmosphere in arbitrary temperature of 800 DEG C ~ 1050 DEG C of temperature ranges, prepare rich lithium solid solution cathode material.
2. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion 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 preparation method of the rich lithium solid solution cathode material of doping trivalent ion according to claim 1, is characterized in that 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.
4. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion according to claim 1, is characterized in that 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.
5. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion according to claim 1, is characterized in that 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.
6. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion according to claim 1, is characterized in that the compound of described M is Sc 2o 3, Sc 2(CO 3) 3, Sc (NO 3) 3, Sc (OH) 3, Cr 2o 3, Cr (OH) 3, Cr (NO 3) 3, Al (NO 3) 3, Al 2o 3or Al (OH) 3.
7. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion according to claim 1, it is characterized in that described vacuumize is by the arbitrary temperature of predecessor 1 80 DEG C ~ 280 DEG C of temperature ranges, prepare predecessor 2 in the arbitrary vacuum under pressure drying between 10Pa ~ 10132Pa pressure range.
8. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion according to claim 1, is characterized in that described spraying dry is the arbitrary temperature 110 DEG C ~ 280 DEG C of temperature ranges, adopts the predecessor 2 that spray dryer preparation is dry.
9. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion 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 that oxygen volume content is greater than 21% and is less than the gas between 100%.
10. the preparation method of the rich lithium solid solution cathode material of doping trivalent ion according to claim 1, is characterized in that described wet-milling mixing, general milling machine, super ball mill or wet milk carries out; The compound of described lithium is lithium carbonate, lithium hydroxide or Lithiagel, or the mixture of its arbitrary proportion.
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US9716265B2 (en) 2014-08-01 2017-07-25 Apple Inc. High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries
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US11695108B2 (en) 2018-08-02 2023-07-04 Apple Inc. Oxide mixture and complex oxide coatings for cathode materials
US11749799B2 (en) 2018-08-17 2023-09-05 Apple Inc. Coatings for cathode active materials
US11757096B2 (en) 2019-08-21 2023-09-12 Apple Inc. Aluminum-doped lithium cobalt manganese oxide batteries
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Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
US7678503B2 (en) * 2006-09-25 2010-03-16 Board Of Regents, The University Of Texas Systems Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss
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