CN102881875B - Method for preparing lithium-rich solid solution cathode material doped with divalent ions through partial dissolution - Google Patents

Method for preparing lithium-rich solid solution cathode material doped with divalent ions through partial dissolution Download PDF

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CN102881875B
CN102881875B CN201210391441.XA CN201210391441A CN102881875B CN 102881875 B CN102881875 B CN 102881875B CN 201210391441 A CN201210391441 A CN 201210391441A CN 102881875 B CN102881875 B CN 102881875B
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compound
carbonate
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solid solution
cathode material
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CN102881875A (en
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童庆松
蔡斌
周惠
肖斌
韩铭
黄娟
姜祥祥
潘樱
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Fujian Normal University
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    • 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
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Abstract

The invention relates to a method for preparing a lithium-rich solid solution cathode material doped with divalent ions through partial dissolution. The method is characterized by comprising the following steps of: weighing a lithium compound, a nickel compound, a manganese compound, a cobalt compound and an M compound in a molar ratio of lithium ions to nickel ions to manganese ions to cobalt ions to M ions of (1.1+0.90.x):(1-x).y:(x+z-x.z):(1-x).k:(1-x).q; mixing the weighed nickel compound, manganese compound, cobalt compound and M compound, adding a wet grinding medium and weak organic acid, performing wet grinding and mixing for 3 to 15 hours, adding the lithium compound, and performing wet grinding and mixing to obtain a precursor 1; and drying the precursor 1, putting the precursor 1 in air, oxygen-rich gas or pure oxygen atmosphere, and sintering to prepare the lithium-rich solid solution cathode material. The electrode material prepared by the method has uniform composition, high discharge performance, and high discharge cycle performance particularly under the high-current condition.

Description

Be partly dissolved the method for the bivalent ions rich lithium solid solution cathode material of the standby doping of legal system
Technical field
The invention belongs to technical field prepared by battery electrode material, 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 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 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 that specific capacity is high, the advantage such as Heat stability is good, cycle performance are good, thereby 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, the difference of the precipitation that foundation generates is divided into again hydroxide coprecipitation step and carbonate coprecipitation method.
In hydroxide coprecipitation step, according to the difference that adopts 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, through one section or two sections or twice sintering, make rich lithium lithium manganate material [Guo X. et al. J. Power Sources, 2008,184:414 – 419.; 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 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.].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 ℃ 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 the synthetic LiNi of the LiOH of dry hydroxide and excessive 3% xmn xco (1 – 2x)o 2predecessor.After 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 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, through double sintering, make rich lithium layered cathode material.[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.By coprecipitation, first prepare not coated sample, then by solution route, prepare surface by Al 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 minute 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 ℃ after sintering again with Li 2cO 3mix, at air atmosphere, in 900 ℃ of sintering, obtain spherical powder Li 1.167ni 0.2co 0.1mn 0.533o 2.In 2.0 – 4.8 V voltage range discharge capacities, can reach 340mAh/g.[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 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 ℃ after filtering, sintering at 400 ℃, 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 ℃, 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 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, respectively at 550 ℃ and 850 ℃ of sintering, make 0.5Li 2mnO 30.5LiCoO 2predecessor.This predecessor is mixed with ammonium dihydrogen phosphate, glycolic, nickel nitrate, lithium nitrate, dry in air atmosphere, then at 550 ℃ 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.].
Owing to preparing by coprecipitation method, the co-precipitation that no matter forms hydroxide still forms the co-precipitation of carbonate, and 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 water pollution.While preparing carbonate deposition by coprecipitation, the precipitation solubility product of nickel, manganese, cobalt ions is larger; While preparing precipitation of hydroxide by coprecipitation, partly precipitated dissolve and the precipitation that causes nickel, manganese, cobalt ions not exclusively (precipitation of hydroxide thing easily and OH -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 preparing is at present all undesirable, the present invention attempts by adding dopant further to improve heavy-current discharge performance in preparation process.
In sum, the preparation process of the power consumptions such as the filtration that will experience when prepared by coprecipitation, washing, water consumption, in addition, when being prepared by coprecipitation, because hydroxide or the carbonate deposition of manganese ion, cobalt ions, nickel ion are incomplete, make the stoichiometric proportion of preparing product be difficult to control.Common solid sintering technology mixes by the simple ball milling of product, then carry out reactant that technique prepared by sintering exists mix inhomogeneous, the problem such as the chemical property consistency of product is poor.
Summary of the invention
For avoiding the deficiencies in the prior art, the technical solution adopted in the present invention is:
(1) according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions, M ion, be (1.1+0.90x): (1-x) y: (x+z-xz): (1-x) k: (1-x) q take respectively the compound of lithium, the compound of the compound of nickel, manganese, the compound of cobalt and M compound; According to following molar ratio relation, measure organic monoacid: (x+z-xz)≤organic monoacid molal quantity≤x+(1-x) (z+y+k+q); 2y+4z+3k+2q-2.9=0, and the span of x, y, z, q, k meets following relation simultaneously: 0.25≤x≤0.55,0.05≤y≤0.50,0.18≤z≤0.40,0.02≤q≤0.15,0.05≤k≤0.30.
(2) by the compound of the compound of the compound of the nickel taking, manganese, cobalt and M compound, the 1/10 times of wet grinding media to 10 times of volumes that adds total solid capacity, add organic monoacid, wet-milling mixes 3 hours～15 hours, the compound that adds again lithium, wet-milling mixing obtains predecessor 1 for 3 hours～15 hours; Predecessor 1 use vacuumize or spray-dired method are prepared to dry predecessor 2; Predecessor 2 is placed in to 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 to air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, is cooled to room temperature and makes parent Preburning material; After parent Preburning material is pulverized and being sieved, be again placed in 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 carried out as follows: predecessor 2 is placed in to air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, then be placed in the sintering furnace of 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 that cationic chemical valence is oxide, hydroxide, carbonate, chloride, nitrate or the fluoride of magnesium, zinc or the calcium of divalence.Described M ion is magnesium, zinc or calcium ion.
Described vacuumize is the arbitrary temperature 80 ℃～280 ℃ of temperature ranges by predecessor 1, the dry predecessor 2 of preparing under the vacuum between 10Pa～10132Pa pressure; Described spraying is dry is the arbitrary temperature 110 ℃～280 ℃ of temperature ranges, adopts spray dryer to prepare dry predecessor 2.
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 22% and be less than the gas between 100%.
Described wet-milling equipment 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, due to rich lithium solid solution xLi 2mnO 3(1-x) Li[Li 0.10ni ymn zco km q] O 2in structure under different preparation conditions, when even only preparation technology is different, also usually there is ion mixing phenomenon in lithium position, manganese position, nickel position and cobalt position ion, has a strong impact on the chemical property of preparing sample.In order to prevent that in rich lithium solid solution structure, nickel position is replaced by other valence state ion, cause the unsteadiness of sample structure in charge and discharge process, the present invention is doped into bivalent cation in rich lithium solid solution structure, prevent the generation of other valence state ion mixing phenomenon in charge and discharge process, stablize the structure of rich lithium solid solution, improved and prepared the cycle performance of sample under 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, consuming time few, and the electrode material of preparation forms evenly, has outstanding discharge performance, and the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Accompanying drawing explanation
Fig. 1 is the sample XRD diffraction pattern of the embodiment of the present invention 3 preparations.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed.Embodiment further supplements and explanation of the present invention, rather than the restriction to invention.
Embodiment 1
According to lithium ion, nickel ion, manganese ion, cobalt ions, zinc ion, formic acid mol ratio, be 1.595:0.023: 0.73: 0.135:0.0675:0.73 takes respectively lithium carbonate, nickelous carbonate, manganese carbonate, cobalt carbonate, ZnO and formic acid.
The nickelous carbonate taking, manganese carbonate, cobalt carbonate and ZnO are mixed, add the deionized water of 10 times of volumes of total solid capacity, add formic acid, mix 3 hours, then add lithium carbonate with the wet-milling of general milling machine, wet-milling mixing obtains predecessor 1 for 3 hours; Predecessor 1 is at 80 ℃, dry under the vacuum condition of 10Pa pressure, prepares predecessor 2.Predecessor 2 is placed in to air atmosphere, and at 300 ℃, sintering is 3 hours, is cooled to room temperature and makes parent Preburning material; Parent Preburning material pulverized and crossed 200 mesh sieves, being again placed in air atmosphere, at 1050 ℃, sintering is 24 hours, and preparation consists of 0.55 Li 2mnO 30.45 Li[Li 0.10ni 0.05mn 0.40co 0.30zn 0.15] O 2rich lithium solid solution cathode material.When preparing sample and discharging and recharging at 47 ℃, at 4.6 to 2.5V voltage ranges, under 0.95C electric current, the discharge capacity of the 1st circulation is 142mAh/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, consuming time few, and the electrode material of preparation forms 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
According to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions, magnesium ion, oxalic acid, be 1.595:0.225: 0.64: 0.12:0.0675:1.05 takes respectively Lithiagel, basic nickel carbonate, basic carbonate manganese, basic cobaltous carbonate, MgO and oxalic acid.
The basic nickel carbonate taking, basic carbonate manganese, basic cobaltous carbonate and MgO are mixed, the ethanol that adds 1/10 times of volume of total solid capacity, adds oxalic acid, with super ball mill wet-milling, mixes 15 hours, add again Lithiagel, with super ball mill ball milling, mix and within 15 hours, obtain predecessor 1; Predecessor 1 is prepared to dry predecessor 2 with spray dryer at 110 ℃.Predecessor 2 is placed in to the oxygen-enriched air gas atmosphere of oxygen volume content 22%, at 300 ℃, sintering is 3 hours, the sintering furnace that is then placed in another air atmosphere sintering 3 hours at 1050 ℃, and preparation consists of 0.55 Li 2mnO 30.45 Li[Li 0.1ni 0.50mn 0.20co 0.267mg 0.15] O 2rich lithium solid solution cathode material.When preparing sample and discharging and recharging at 47 ℃, at 4.6 to 2.5V voltage ranges, under 0.95C electric current, the discharge capacity of the 1st circulation is 125mAh/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, consuming time few, and the electrode material of preparation forms 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
According to lithium ion, nickel ion, manganese ion, cobalt ions, magnesium ion, acetic acid mol ratio, it is 1.325: 0.375: 0.55: 0.065:0.015:0.55 takes respectively lithium hydroxide, nickelous carbonate, manganese carbonate, basic cobaltous carbonate, Mg (OH) 2, acetic acid.
By the nickelous carbonate taking, manganese carbonate, basic cobaltous carbonate and Mg (OH) 2mix, add the acetone of 10 times of volumes of total solid capacity, add acetic acid, with wet milk wet-milling, mix 15 hours, then add lithium hydroxide, with wet milk wet-milling, mix and within 15 hours, obtain predecessor 1; At 280 ℃, in the vacuum of 10132 Pa pressure, be dried and prepare predecessor 2.Predecessor 2 is placed in to the oxygen-enriched air gas atmosphere of oxygen volume content 99%, at 550 ℃, sintering is 15 hours, is then placed in the sintering furnace of the oxygen-enriched air atmosphere of another oxygen volume content 99%, and at 800 ℃, sintering is 24 hours, and preparation consists of 0.25 Li 2mnO 30.75 Li[Li 0.10ni 0.15mn 0.40co 0.233mg 0.15] O 2rich lithium solid solution cathode material.Prepare the XRD diffraction pattern of sample as shown in Figure 1.When preparing sample and discharging and recharging at 47 ℃, at 4.6 to 2.5V voltage ranges, under 0.95C electric current, the discharge capacity of the 1st circulation is 165mAh/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, consuming time few, and the electrode material of preparation forms 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
According to lithium ion, nickel ion, manganese ion, cobalt ions, zinc ion, oxalic acid mol ratio, be mixture, basic cobaltous carbonate, the ZnCl of 1.325:0.375:0.541: the 0.0375:0.075:0.60 mixture, basic carbonate manganese and the manganese carbonate weight ratio 1:9 that take respectively lithium carbonate, basic nickel carbonate and nickelous carbonate weight ratio 1:1 2, oxalic acid.
By mixture, basic cobaltous carbonate and the ZnCl of the mixture of the basic nickel carbonate taking and nickelous carbonate weight ratio 1:9, basic carbonate manganese and manganese carbonate weight ratio 1:9 2mix, add the deionized water of 3 times of volumes of total solid capacity, add oxalic acid, with the wet-milling of general milling machine, mix 10 hours, then add lithium carbonate, with wet milk, mix and within 15 hours, obtain predecessor 1; Predecessor 1 is dried to the dry predecessors 2 of preparation 110 ℃ of sprayings.Predecessor 2 is placed in to air atmosphere, 550 ℃ of sintering 15 hours, is cooled to room temperature and makes parent Preburning material; Parent Preburning material pulverized and crossed 100 mesh sieves, being again placed in air atmosphere, at 800 ℃, sintering is 24 hours, and preparation consists of 0.25 Li 2mnO 30.75 Li[Li 0.10ni 0.50mn 0.3875co 0.05zn 0.10] O 2rich lithium solid solution cathode material.When preparing sample and discharging and recharging at 47 ℃, at 4.6 to 2.5V voltage ranges, under 0.95 C electric current, the discharge capacity of the 1st circulation is 179mAh/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, consuming time few, and the electrode material of preparation forms 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
Preparation is comprised of following steps:
According to lithium ion, nickel ion, manganese ion, cobalt ions, zinc ion, acetic acid mol ratio, be 1.325: 0.038:0.625: 0.19:0.015:0.80 takes respectively mixture, the Zn (NO of lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:9 3) 2, acetic acid.
By mixture, the Zn (NO of the nickelous carbonate taking, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:9 3) mix, add the distilled water of 7 times of volumes of total solid capacity, add acetic acid, with wet milk, mix 11 hours, then add lithium hydroxide, with general milling machine, mix and within 12 hours, obtain predecessor 1; Predecessor 1 is prepared to dry predecessor 2 at 280 ℃ with spray dryer.Predecessor 2 is placed in to pure oxygen atmosphere, and at 500 ℃, sintering is 10 hours, is cooled to room temperature and makes parent Preburning material; Parent Preburning material is pulverized and crossed after 80 mesh sieves, be again placed in pure oxygen atmosphere, at 1000 ℃, sintering is 12 hours, and preparation consists of 0.25Li 2mnO 30.75 Li[Li 0.10ni 0.050mn 0.50co 0.253zn 0.02] O 2rich lithium solid solution cathode material.When preparing sample and discharging and recharging at 47 ℃, at 4.6 to 2.5V voltage ranges, under 0.95C electric current, the discharge capacity of the 1st circulation is 197mAh/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, consuming time few, and the electrode material of preparation forms 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
According to lithium ion, nickel ion, manganese ion, cobalt ions, calcium ion, formic acid mol ratio, it is 1.37: 0.070: 0.608: 0.21:0.014: 0.90 takes respectively mixture, the CaF of lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1 2, formic acid.
By mixture, the CaF of the nickelous carbonate taking, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1 2mix, add the acetone of 6 times of volumes of total solid capacity, add formic acid, wet-milling mixes 15 hours, then adds lithium hydroxide, and wet-milling mixing obtains predecessor 1 for 3 hours; At 200 ℃, with spray dryer, prepare dry predecessor 2.Predecessor 2 is placed in to the oxygen-enriched air gas atmosphere of oxygen volume content 70%, at 400 ℃, sintering is 15 hours, is then placed in the sintering furnace of oxygen-enriched air gas atmosphere of another oxygen volume content 30% in 950 ℃ of sintering 7 hours, and preparation consists of 0.30 Li 2mnO 30.70 Li[Li 0.10ni 0.10mn 0.44co 0.30ca 0.02] O 2rich lithium solid solution cathode material.When preparing sample and discharging and recharging at 47 ℃, at 4.6 to 2.5V voltage ranges, under 0.95 C electric current, the discharge capacity of the 1st circulation is 203mAh/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, consuming time few, and the electrode material of preparation forms 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
According to lithium ion, nickel ion, manganese ion, cobalt ions, calcium ion, formic acid mol ratio, it is 1.37: 0.070: 0.608: 0.21:0.014: 0.90 takes respectively mixture, the CaF of lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1 2, formic acid.
By mixture, the CaF of the nickelous carbonate taking, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:9 2mix, add the acetone of 6 times of volumes of total solid capacity, add formic acid, wet-milling mixes 15 hours, then adds lithium hydroxide, and wet-milling mixing obtains predecessor 1 for 3 hours; At 280 ℃, with spray dryer, prepare dry predecessor 2.Predecessor 2 is placed in to air atmosphere, and at 450 ℃, sintering is 10 hours, and the sintering furnace that is then placed in another pure oxygen atmosphere was in 1050 ℃ of sintering 7 hours, and preparation consists of 0.30 Li 2mnO 30.70 Li[Li 0.10ni 0.10mn 0.44co 0.30ca 0.02] O 2rich lithium solid solution cathode material.
Compare 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 of preparation forms evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.
Embodiment 8
According to lithium ion, nickel ion, manganese ion, cobalt ions, calcium ion, formic acid mol ratio, it is 1.37: 0.070: 0.608: 0.21:0.014: 0.90 takes respectively mixture, the CaF of lithium hydroxide, nickelous carbonate, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 9:1 2, formic acid.
By mixture, the CaF of the nickelous carbonate taking, basic carbonate manganese, basic cobaltous carbonate and cobalt carbonate weight ratio 1:1 2mix, add the acetone of 6 times of volumes of total solid capacity, add formic acid, wet-milling mixes 10 hours, then adds lithium hydroxide, and wet-milling mixing obtains predecessor 1 for 3 hours; At 200 ℃, in 500Pa vacuum under pressure, be dried the dry predecessor 2 of preparation.Predecessor 2 is placed in to purity oxygen atmosphere, and at 400 ℃, sintering is 15 hours, is cooled to room temperature and makes parent Preburning material.Parent Preburning material is pulverized and crossed after 150 mesh sieves, be again placed in and be then placed in 950 ℃ of sintering 7 hours, preparation consists of 0.30 Li 2mnO 30.70 Li[Li 0.10ni 0.10mn 0.44co 0.30ca 0.02] O 2rich lithium solid solution cathode material.
Compare 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 of preparation forms evenly, have outstanding discharge performance, the cycle performance particularly discharging under large current condition is good, for industrialization is laid a good foundation.

Claims (9)

1. the method that is partly dissolved the bivalent ions rich lithium solid solution cathode material of the standby doping of legal system, is characterized in that preparation process is comprised of following steps:
(1) according to the mol ratio of lithium ion, nickel ion, manganese ion, cobalt ions, M ion, be (1.1+0.90x): (1-x) y: (x+z-xz): (1-x) k: (1-x) q take respectively the compound of lithium, the compound of the compound of nickel, manganese, the compound of cobalt and M compound; According to following molar ratio relation, measure organic monoacid: (x+z-xz)≤organic monoacid molal quantity≤x+(1-x) (z+y+k+q); 2y+4z+3k+2q-2.9=0, and the span of x, y, z, q, k meets following relation simultaneously: 0.25≤x≤0.55,0.05≤y≤0.50,0.18≤z≤0.40,0.02≤q≤0.15,0.05≤k≤0.30; Described M compound is oxide, hydroxide, carbonate, chloride, nitrate or the fluoride of magnesium, zinc or calcium; Described M ion is magnesium, zinc or calcium ion;
(2) by the compound of the compound of the compound of the nickel taking, manganese, cobalt and M compound, the 1/10 times of wet grinding media to 10 times of volumes that adds total solid capacity, add organic monoacid, wet-milling mixes 3 hours～15 hours, the compound that adds again lithium, wet-milling mixing obtains predecessor 1 for 3 hours～15 hours; Predecessor 1 use vacuumize or spray-dired method are prepared to dry predecessor 2; Predecessor 2 is placed in to 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 to air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, is cooled to room temperature and makes parent Preburning material; After parent Preburning material is pulverized and being sieved, be again placed in 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 carried out as follows: predecessor 2 is placed in to air, oxygen rich gas or pure oxygen atmosphere, arbitrary temperature sintering of 300 ℃～550 ℃ of temperature ranges 3 hours～15 hours, then be placed in another sintering furnace that passes into 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 bivalent ions rich lithium solid solution cathode material of the standby doping 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 bivalent ions rich lithium solid solution cathode material of doping, 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 bivalent ions rich lithium solid solution cathode material of doping, 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 bivalent ions rich lithium solid solution cathode material of doping, 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 bivalent ions rich lithium solid solution cathode material of doping, it is characterized in that described vacuumize is the arbitrary temperature 80 ℃～280 ℃ of temperature ranges by predecessor 1, the dry predecessor 2 of preparing under the vacuum between 10Pa～10132Pa pressure.
7. the legal system that is partly dissolved according to claim 1 is for the method for the bivalent ions rich lithium solid solution cathode material of doping, it is characterized in that it is the arbitrary temperature 110 ℃～280 ℃ of temperature ranges that described spraying is dried, and adopts spray dryer to prepare dry predecessor 2.
8. the method that is partly dissolved the bivalent ions rich lithium solid solution cathode material of the standby doping 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 that oxygen volume content is greater than 21% and be less than the gas between 100%.
9. the method that is partly dissolved the bivalent ions rich lithium solid solution cathode material of the standby doping of legal system according to claim 1, is characterized in that described wet-milling equipment 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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