CN103178254A - Co-doped lithium vanadate positive material and preparation method thereof - Google Patents
Co-doped lithium vanadate positive material and preparation method thereof Download PDFInfo
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- CN103178254A CN103178254A CN201310079443XA CN201310079443A CN103178254A CN 103178254 A CN103178254 A CN 103178254A CN 201310079443X A CN201310079443X A CN 201310079443XA CN 201310079443 A CN201310079443 A CN 201310079443A CN 103178254 A CN103178254 A CN 103178254A
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Abstract
The invention relates to a lithium ion battery positive material LiV3-x-yYx ZryO8 and a preparation method thereof; the method comprises the following step of: adopting a lithium source, a vanadium source and a compound containing doped elements yttrium and zirconium to prepare the lithium ion battery positive material LiV3-x-yYxZryO8 with a layered structure by a special formulation and improved solid-phase reaction, wherein x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 0.2, and the solid-phase reaction conditions are as follows: thee air atmosphere is heated up to be at 400-900 DEG C and raw materials are placed in cold air for quenching. The obtained positive material has the specific discharge capacity of more than 225mAh/g, is good in circulation performance, and has the specific discharge capacity maintained to be more than 210mAh/g after 50-time circulation.
Description
Technical field
The present invention relates to the lithium ion battery material field, particularly, the present invention relates to lithium vanadate anode material of a kind of codope and preparation method thereof.
Background technology
Lithium ion battery is the important devices in present energy storage field, and positive electrode is again the critical material that consists of lithium ion battery.It is high that lithium vanadate has a charging and discharging capacity, good reversibility, and the advantages such as good cycle have huge business development potentiality.But it also has and embeds and deviate from the shortcomings such as process complexity, voltage platform be not obvious, how to improve its stability and cyclic reversibility, becomes the obstacle of lithium vanadate material large-scale application.
From (Crystal chemstry of non-stoimetric pentavalent vanadium oxides:crystal structure of Li such as nineteen fifty-seven Wadsley
1+xV
3O
8.Acta Crystallographica, 1957,10 (4): 261-267) taken the lead in reporting the crystal structure of lithium vanadate, pointed out that it can be used as anode material for lithium-ion batteries.Many researchers is explored this, and the people such as Qin Honglian (lithium vanadate anode material of the standby Doped with Titanium of middle thermosetting phase legal system. power technology, 2010, (11): 1121-1123) with Li
2CO
3And V
2O
5Be raw material, in using, thermosetting phase legal system is for doped Ti
4+Anode material for lithium-ion batteries Li
1.1V
3-yTi
yO
8(y=0.05,0.1,0.2), result shows, doped Ti
4+The chemical property of hot solid phase method product in can improving well, after doping, the position of the X diffraction maximum of sample does not change, and illustrates that doping does not change the structure of sample.Patent publication No. is that the patent " method of method for preparing lithium vanadate by microwave " of CN101348278A utilizes this energy of microwave to prepare the lithium vanadate material, raw material is put into corundum crucible, crucible is placed in the container that carbon dust is housed, and cover the lid of the loose attached carbon dust in surface, and then reaction 30s to 5min under microwave, namely obtain product.It is high that the method has production efficiency, and power consumption is few.Patent publication No. is that the patent " a kind of low-temperature synthetic method of long life lithium vanadate " of CN101503213A first will contain lithium and vanadium-containing compound react 0.5～1h in water, then dry 1～24h under 120 ℃ carries out annealing in process 0.5～5h under 100～400 ℃ and obtains product.The method easy operating, flow process is simple, the product of the metering ratio that is easy to get, but special capacity fade is very fast, and after 100 circulations, specific capacity reduces by 15% left and right, and after adding the modifier such as zirconium powder, after 100 circulations, specific capacity only reduces by 4% left and right.Patent publication No. is that the patent " three-dimensional porous lithium vanadate anode material and preparation method thereof " of CN102299312A is with LiOHH
2O, NH
4VO
3Add in deionized water with glycine, after mix and blend, drying obtains precursor powder, then sintering obtains product in air, and this product first charge-discharge specific capacity reaches 218～237mAh/g, volume lowering 18% left and right after 50 circulations, and cyclical stability is relatively poor.
Studies show that, doping can produce significant impact to the performance of material.As people (Preparation and electrochemical properties of Zr-doped LiV such as Zhongxiang City
3O
8Cathode materials for lithium-ion batteries[J] .Journal of Solid State Electrochemistry, 2012,16:2135-2141) the doping Zr of preparation
4+Lithium vanadate anode material LiV
3-yZr
yO
8, find that material exists with solid gel form, due to Zr when 0＜y＜0.08
4+Ionic radius greater than V
5+, Zr
4+Ion makes interlaminar action power strengthen, thereby material electrochemical performance and cyclical stability all increase, but inserts Zr
4+Make the lithium vanadate interlamellar spacing increase, thereby make the impedance of material obviously reduce.As people (Y such as Liu Yongmei
3+, F
-The research of the electrochemistry of codope lithium vanadate material and storing performance. the material Leader, 2011,25 (17): 304-309) studies show that, the impurity that doping is introduced is non-electro-chemical activity, and the codope sample has more lithium ion embedding dislocation to put and better cyclical stability.But, Y
3+, F
-Codope energy " contraction " lattice is unfavorable for the diffusion of lithium ion, affects the high rate performance that material discharges and recharges.
Therefore, develop charging and discharging capacity and cycle performance all good lithium vanadate anode material be the technical barrier in this field.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of lithium vanadate anode material, and it reaches the dual purpose that increases charging and discharging capacity and material cyclical stability by codope yttrium and zr element.
Described lithium vanadate anode material is LiV
3-x-yY
xZr
yO
8, have layer structure, wherein, 0＜x≤0.2, and 0＜y≤0.2.
Described x can be 0.001,0.002,0.005,0.01,0.02,0.05,0.09,0.11,0.14,0.16,0.18 or 0.19 etc., preferred 0＜x≤0.15, particularly preferably 0＜x≤0.1.
Described y can be for 0.001,0.002,0.005,0.01,0.02,0.05,0.09,0.11,0.14,0.16,0.0.18 or 0.19 etc., preferred 0＜y≤0.15, particularly preferably 0＜y≤0.1.
Particularly preferably, described lithium vanadate anode material is LiV
3-x-yY
xZr
yO
8, wherein, 0＜x≤0.1, and 0＜y≤0.1.
One of purpose of the present invention also is to provide a kind of lithium ion battery.Described lithium ion battery contains described lithium vanadate anode material.
One of purpose of the present invention also is to provide a kind of preparation method of described lithium vanadate anode material, and described method technique is simple, is fit to mass production, and the positive electrode of preparation is Y
3+And Zr
4+The binary co-doped material, its chemical property and cyclical stability are good.
The preparation method of described lithium vanadate anode material comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, drying is warming up to 400～900 ℃ of sintering, and is cooling, obtains described lithium vanadate anode material.
Preferably, the preparation method of described lithium vanadate anode material comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, drying is pulverized, and is warming up to 400～900 ℃ of sintering, arrives after sintering temperature coolingly, obtains described lithium vanadate anode material.
Preferably, the preparation method of described lithium vanadate anode material comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, and drying, compressing, be warming up to 400～900 ℃ of sintering, arrive after sintering temperature coolingly, obtain described lithium vanadate anode material.
Preferably, the preparation method of described lithium vanadate anode material comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, drying, pulverize, compressing, be warming up to 400～900 ℃ of sintering, cooling after the arrival sintering temperature, obtain described lithium vanadate anode material.
preferably, described lithium source is lithium dihydrogen phosphate, lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium nitrate, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium oxalate, 1 kind or the combination of at least 2 kinds in lithium sulfate, the typical but non-limiting example of described combination has: the combination of lithium dihydrogen phosphate and lithium carbonate, the combination of lithium carbonate and lithium acetate, the combination of lithium chloride and lithium nitrate, lithium acetate, the combination of lithium formate and lithium citrate, lithium hydroxide, the combination of tert-butyl alcohol lithium and lithium oxalate, lithium nitrate, lithium bromide, the combination of lithium hydroxide and tert-butyl alcohol lithium, lithium hydroxide, tert-butyl alcohol lithium, the combination of lithium benzoate and phosphoric acid hydrogen two lithiums, lithium phosphate, phosphoric acid hydrogen two lithiums, the combination of lithium oxalate and lithium sulfate, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, the combination of lithium phosphate and phosphoric acid hydrogen two lithiums, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, the combination of lithium phosphate and phosphoric acid hydrogen two lithiums, lithium bromide, lithium hydroxide, the combinations of tert-butyl alcohol lithium etc. are particularly preferably lithium hydroxide, lithium carbonate, 1 kind or the combination of at least 2 kinds in lithium acetate or lithium oxalate.
preferably, described vanadium source is the carbonic acid vanadium, vanadium tetrachloride, the dichloro vanadyl, oxalic acid is crossed vanadyl, vanadium trioxide, vanadium trifluoride, vanadic oxide, 1 kind or the combination of at least 2 kinds in vanadium dioxide or ammonium metavanadate, the typical but non-limiting example of described combination comprises: the combination of carbonic acid vanadium and vanadium tetrachloride, the combination of dichloro vanadyl and vanadium trifluoride, vanadium trioxide, the combination of vanadic oxide and vanadium dioxide, oxalic acid is crossed vanadyl, the combination of vanadium trioxide and vanadium trifluoride, vanadium tetrachloride, the dichloro vanadyl, oxalic acid is crossed vanadyl, the combination of vanadium trioxide and vanadium trifluoride, oxalic acid is crossed vanadyl, vanadium trioxide, vanadium trifluoride, vanadic oxide, the combination of vanadium dioxide and ammonium metavanadate etc., be particularly preferably vanadic oxide, 1 kind or the combination of at least 2 kinds in vanadium dioxide or ammonium metavanadate.
Preferably, described zirconium source is zirconium hydroxide (Zr (OH)
3And/or Zr (OH)
4), a kind or the combination of at least 2 kinds in zirconium carbonate ammonium, zirconium chloride, zirconium sulfate, zirconium dioxide, acetic acid zirconium, zirconium nitrate or oxalic acid zirconium, the typical but non-limiting example of described combination comprises: Zr (OH)
3With the combination of zirconium carbonate ammonium, the combination of zirconium sulfate and zirconium dioxide, the combination of zirconium chloride, zirconium sulfate and zirconium dioxide, the combination of zirconium dioxide, acetic acid zirconium, zirconium nitrate and oxalic acid zirconium, Zr (OH)
4, zirconium carbonate ammonium, zirconium chloride, zirconium sulfate and acetic acid zirconium combination, the combinations of zirconium carbonate ammonium, zirconium chloride, zirconium sulfate, acetic acid zirconium, zirconium nitrate and oxalic acid zirconium etc. are particularly preferably a kind or the combination of at least 2 kinds in zirconium dioxide, acetic acid zirconium, zirconium nitrate or oxalic acid zirconium.
preferably, described yttrium source is yttrium chloride, yttrium hydroxide, yttrium carbonate, yttria, the acetic acid yttrium, 1 kind or the combination of at least 2 kinds in yttrium nitrate or yttrium oxalate, the typical but non-limiting example of described combination comprises: the combination of yttrium chloride and yttrium hydroxide, the combination of acetic acid yttrium and yttrium nitrate, yttrium carbonate, the combination of yttria and acetic acid yttrium, yttrium hydroxide, yttrium carbonate, the combination of yttria and yttrium nitrate, yttrium chloride, yttrium hydroxide, yttrium carbonate, the combination of yttrium nitrate and yttrium oxalate, yttrium chloride, yttrium hydroxide, yttrium carbonate, yttria, the combination of acetic acid yttrium and yttrium nitrate etc., be particularly preferably yttria, the acetic acid yttrium, 1 kind or the combination of at least 2 kinds in yttrium nitrate or yttrium oxalate.
Preferably, the medium that described wet-milling is adopted is water and/or organic solvent, more preferably water, C
1-C
5Alcohols, C
3-C
71 kind or the combination of at least 2 kinds in ketone, halogenated alkane, aromatic compound, more preferably water, ethanol, acetone, CCl
4, a kind or the combination of at least 2 kinds in toluene, described combination typical case but the example of non-limit have: the combination of water and ethanol, the combination of acetone and toluene, acetone, CCl
4, toluene combination etc., be particularly preferably ethanol.
Preferably, abrading-ball in described wet-milling: material: the volume ratio of medium is (3～12): 1:(0.5～6), (5～10): 1:(1～4 more preferably), be particularly preferably 7:1:2.
Preferably, described wet-milling rotating speed is 150～800r/min, and more preferably 200～600r/min, be particularly preferably 250～500r/min.
Preferably, the described wet-milling time is at least 1 hour, more preferably 2～15 hours, is particularly preferably 4～10 hours.
Preferably, described drying is carried out in vacuum drying chamber.
Preferably, described baking temperature is 5～120 ℃, more preferably 15～110 ℃, is particularly preferably 25～100 ℃.
Preferably, be at least 0.5 hour described drying time, more preferably 0.8～32 hour, is particularly preferably 1～24 hour.
Preferably, described pulverizing is for grinding.
Preferably, described compressing for adopting tablet press machine to be compressed to sheet, particularly preferably adopt tablet press machine to be compressed to the sheet that thickness is 0.2～1cm.
Preferably, described compressing pressure is 5～35Mpa, and more preferably 8～25Mpa, be particularly preferably 10～20Mpa.
Preferably, described sintering carries out in Muffle furnace.
Preferably, described programming rate be 15 ℃/below min, such as 0.01 ℃/min, 0.05 ℃/min, 0.09 ℃/min, 0.11 ℃/min, 0.15 ℃/min, 0.2 ℃/min, 0.5 ℃/min, 0.9 ℃/min, 1.1 ℃/min, 1.5 ℃/min, 2 ℃/min, 4 ℃/min, 6 ℃/min, 8 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 14 ℃/min, 14.5 ℃/min, 14.8 ℃/min or 14.9 ℃/min etc., more preferably 0.1～10 ℃/min, be particularly preferably 1～5 ℃/min.
Preferably, described sintering temperature is 450～750 ℃, is particularly preferably 500～680 ℃.
Preferably, described coolingly carry out under cold dry air.
Preferably, describedly pulverize and sieve after cooling, then particularly preferably cooling rear grinding crosses 200 mesh sieves; Preferably, agate mortar is adopted in described grinding.
Preferably, described grind successively after cooling and dry; Preferably, described drying is vacuumize.
Preferably, the preparation method of described lithium vanadate anode material comprises:
(1) with after lithium source, vanadium source, the abundant mixed grinding in zirconium source and yttrium source, add ball-milling medium, after ball milling under 5～120 ℃ of conditions drying 0.5h at least, then be pressed into the disk that thickness is 0.2～1cm under 5～35MPa pressure;
(2) disk after suppressing is placed in Muffle furnace, is heated to 400～900 ℃ of sintering, after furnace temperature rises to 400～900 ℃, is placed in cold dry air and quenches, and grinds, and crosses 200 purposes sieves, and then vacuumize obtains lithium vanadate anode material.
Adopt each uniform component distribution of positive electrode of the method for the invention preparation, have excellent chemical property.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the prepared material of the present invention has higher charging and discharging capacity and better electrochemistry cyclical stability, have the reversible discharge capacity greater than 225mAh/g under 0.2C charge-discharge velocity, 10 ℃～35 ℃ conditions, constant current charge-discharge circulation 50 times, reversible discharge capacity is not less than 210mAh/g;
(2) the method for the invention technique is simple, is fit to mass production.
Description of drawings
Fig. 1 makes the scanning electron microscope (SEM) photograph of lithium vanadate material in the embodiment of the present invention 5;
Fig. 2 is the X ray test figure as a result that makes the lithium vanadate material in the embodiment of the present invention 2;
Fig. 3 is electrochemistry stable circulation property testing (charge-discharge test) figure as a result of the lithium vanadate material that makes in the embodiment of the present invention 2.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
7.389g lithium carbonate, 53.508g vanadic oxide, 0.739g zirconium dioxide and 0.677g yttria are ground 30min in mortar after, add 120mL ethanol, put into ball grinder ball milling 6h, obtain yellow slurry, after ball milling under 60 ℃ of conditions dry 12h, obtain yellow block, get dry raw material sample, be pressed into the disk of thick approximately 0.2cm on tablet press machine.The disk of compacting is placed in Muffle furnace, is heated to 600 ℃ of sintering, programming rate is 1 ℃/min.When furnace temperature rises to 600 ℃, the sample of calcining is taken out and is placed in cold dry air (cold dry air be the rustless steel container with a good seal be placed on mixture of ice and water obtain) quenching.Product after quenching porphyrize in agate mortar is crossed 200 purpose sieves, and then 120 ℃ of vacuumize 4h, namely obtain consisting of LiV
2.94Y
0.03Zr
0.03O
8The positive electrode sample.
Test: as positive active material, acetylene black is conductive agent, and PVDF is bonding agent.Positive electrode: conductive agent: bonding agent=90:5:5(weight ratio).Then take aluminium foil as the collector smear, take metal lithium sheet as to electrode, with 1.0mol/L LiPF
6/ EC+DEC(1:1Vol.) be electrolyte, be assembled into the simulation button cell in being full of the stainless steel glove box of argon gas.Then carry out constant current charge-discharge on the Land-2001A battery test system.Voltage range 1.8～3.8V, charge-discharge velocity are 0.2C, and the initial charge specific capacity of this material is 186.80mAh/g, and first discharge specific capacity is 230mAh/g, and efficient reaches 95%.
Embodiment 2
The present embodiment raw material is got 7.389g lithium carbonate, 52.416g vanadic oxide, 1.479g zirconium dioxide and 1.355g yttria, ball milling 10h, and 80 ℃ of vacuumize 6h after ball milling, sintering temperature is 600 ℃, and programming rate is 3 ℃/min, and all the other are with embodiment 1.
The first charge-discharge capacity of specimen material is respectively 225mAh/g, and after constant current charge-discharge circulation 50 times, the specific discharge capacity of material is decay not, and efficiency for charge-discharge remains between 95%～98%.
Embodiment 3
The present embodiment raw material is got 4.790g lithium hydroxide, 51.324g vanadic oxide, 2.218g zirconium dioxide and 2.032g yttria, ball milling 4h, and 100 ℃ of vacuumize 1h, sintering temperature is 680 ℃, and programming rate is 5 ℃/min, and all the other are with embodiment 1.
The first charge-discharge capacity of specimen material is respectively 240mAh/g, and after constant current charge-discharge circulation 50 times, the specific discharge capacity of material still remains on 230mAh/g, and efficiency for charge-discharge remains between 90%～94%.
Embodiment 4
The present embodiment raw material is got 4.790g lithium hydroxide, 52.416g vanadic oxide, 4.071g zirconium nitrate and 4.597g yttrium nitrate, ball milling 10h, and room temperature vacuumize 24h after ball milling, sintering temperature is 600 ℃, all the other are with embodiment 1.
The first charge-discharge capacity of specimen material is respectively 225mAh/g, and after constant current charge-discharge circulation 50 times, the specific discharge capacity of material still remains on 210mAh/g, and efficiency for charge-discharge remains between 90%～94%.
Embodiment 5
The present embodiment raw material is got 4.790g lithium hydroxide, 51.870g vanadic oxide, 5.089g zirconium nitrate and 5.746g yttrium nitrate, ball milling 6h, and 80 ℃ of vacuumize 6h after ball milling, sintering temperature is 680 ℃, all the other are with embodiment 1.
The first charge-discharge capacity of this specimen material is respectively 225mAh/g, and after constant current charge-discharge circulation 50 times, the specific discharge capacity of material still remains on 210mAh/g, and efficiency for charge-discharge remains between 90%～94%.
Embodiment 6
With 6.929g lithium acetate, 53.78g vanadium tetrachloride, 3.185g Zr (OH)
4After the 0.195g yttrium chloride mixes, add 100mL toluene, put into ball grinder ball milling 16h, obtain yellow slurry, after ball milling under 120 ℃ of conditions dry 0.5h, obtain yellow block, get dry raw material sample, be pressed into the disk of thick approximately 1cm on tablet press machine.The disk of compacting is placed in Muffle furnace, is heated to 900 ℃ of sintering, programming rate is 15 ℃/min.When furnace temperature rises to 900 ℃, the sample of calcining is taken out and is placed in cold dry air (cold dry air be the rustless steel container with a good seal be placed on mixture of ice and water obtain) quenching.Product after quenching porphyrize in agate mortar is crossed 200 purpose sieves, and then 40 ℃ of vacuumize 15h, namely obtain consisting of LiV
2.79Y
0.01Zr
0.2O
8The positive electrode sample.
Adopt the method for testing identical with embodiment 1 to test, the first charge-discharge capacity of this specimen material is respectively 228mAh/g, and after constant current charge-discharge circulation 50 times, the specific discharge capacity of material is 212mAh/g, and efficiency for charge-discharge remains between 92%～95%.
Embodiment 7
With 7.585g lithium nitrate, 32.64g ammonium metavanadate, 0.355g Zr (SO
4)
24H
2O adds 220mL ethanol with after the 2.798g yttrium hydroxide mixes, and puts into ball grinder ball milling 2h, obtains yellow slurry, after ball milling under 10 ℃ of conditions dry 40h, obtain yellow block, get dry raw material sample, be pressed into the disk of thick approximately 0.2cm on tablet press machine.The disk of compacting is placed in Muffle furnace, is heated to 450 ℃ of sintering, programming rate is 10 ℃/min.When furnace temperature rises to 450 ℃, the sample of calcining is taken out and is placed in cold dry air (cold dry air be the rustless steel container with a good seal be placed on mixture of ice and water obtain) quenching.Product after quenching porphyrize in agate mortar is crossed 200 purpose sieves, and then 45 ℃ of vacuumize 12h, namely obtain consisting of LiV
2.79Y
0.2Zr
0.01O
8The positive electrode sample.
Adopt the method for testing identical with embodiment 1 to test, the first charge-discharge capacity of this specimen material is respectively 232mAh/g, and after constant current charge-discharge circulation 50 times, the specific discharge capacity of material is 218mAh/g, and efficiency for charge-discharge remains on 91%～94%.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention is to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a lithium vanadate anode material, is characterized in that, described lithium vanadate anode material is LiV
3-x-yY
xZr
yO
8, have layer structure, wherein, 0＜x≤0.2, and 0＜y≤0.2.
2. lithium vanadate anode material as claimed in claim 1, is characterized in that, described x is 0＜x≤0.15, particularly preferably 0＜x≤0.1;
Preferably, described y is 0＜y≤0.15, particularly preferably 0＜y≤0.1;
Particularly preferably, described lithium vanadate anode material is LiV
3-x-yY
xZr
yO
8, wherein, 0＜x≤0.1, and 0＜y≤0.1.
3. a lithium ion battery, is characterized in that, described lithium ion battery contains lithium vanadate anode material as claimed in claim 1 or 2.
4. preparation method of lithium vanadate anode material as claimed in claim 1 or 2 comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, drying is warming up to 400～900 ℃ of sintering, and is cooling, obtains described lithium vanadate anode material.
5. method as claimed in claim 4, is characterized in that, described method comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, drying is pulverized, and is warming up to 400～900 ℃ of sintering, cooling after the arrival sintering temperature, obtain described lithium vanadate anode material;
Preferably, described method comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, and drying, compressing, be warming up to 400～900 ℃ of sintering, arrive after sintering temperature coolingly, obtain described lithium vanadate anode material;
Preferably, described method comprises: press formula ratio with lithium source, vanadium source, zirconium source and yttrium source wet-milling, drying is pulverized, and is compressing, is warming up to 400～900 ℃ of sintering, arrives after sintering temperature coolingly, obtains described lithium vanadate anode material.
6. method as described in claim 4 or 5, it is characterized in that, described lithium source is a kind or the combination of at least 2 kinds in lithium dihydrogen phosphate, lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium nitrate, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium oxalate, lithium sulfate, is particularly preferably a kind or the combination of at least 2 kinds in lithium hydroxide, lithium carbonate, lithium acetate or lithium oxalate;
Preferably, described vanadium source is that carbonic acid vanadium, vanadium tetrachloride, dichloro vanadyl, oxalic acid are crossed a kind or the combination of at least 2 kinds in vanadyl, vanadium trioxide, vanadium trifluoride, vanadic oxide, vanadium dioxide or ammonium metavanadate, is particularly preferably a kind or the combination of at least 2 kinds in vanadic oxide, vanadium dioxide or ammonium metavanadate;
Preferably, described zirconium source is a kind or the combination of at least 2 kinds in zirconium hydroxide, zirconium carbonate ammonium, zirconium chloride, zirconium sulfate, zirconium dioxide, acetic acid zirconium, zirconium nitrate or oxalic acid zirconium, is particularly preferably a kind or the combination of at least 2 kinds in zirconium dioxide, acetic acid zirconium, zirconium nitrate or oxalic acid zirconium;
Preferably, described yttrium source is a kind or the combination of at least 2 kinds in yttrium chloride, yttrium hydroxide, yttrium carbonate, yttria, acetic acid yttrium, yttrium nitrate or yttrium oxalate, is particularly preferably a kind or the combination of at least 2 kinds in yttria, acetic acid yttrium, yttrium nitrate or yttrium oxalate.
7. as the described method of claim 4-6 any one, it is characterized in that, the medium that described wet-milling is adopted is water and/or organic solvent, more preferably a kind or the combination of at least 2 kinds in water, C1-C5 alcohols, C3-C7 ketone, halogenated alkane, aromatic compound, more preferably a kind in water, ethanol, acetone, CCl4, toluene or the combination of at least 2 kinds, be particularly preferably ethanol;
Preferably, abrading-ball in described wet-milling: material: the volume ratio of medium is (3～12): 1:(0.5～6), (5～10): 1:(1～4 more preferably), be particularly preferably 7:1:2;
Preferably, described wet-milling rotating speed is 150～800r/min, and more preferably 200～600r/min, be particularly preferably 250～500r/min;
Preferably, the described wet-milling time is at least 1 hour, more preferably 2～15 hours, is particularly preferably 4～10 hours.
8. as the described method of claim 4-7 any one, it is characterized in that, described drying is carried out in vacuum drying chamber;
Preferably, described baking temperature is 5～120 ℃, more preferably 15～110 ℃, is particularly preferably 25～100 ℃;
Preferably, be at least 0.5 hour described drying time, more preferably 0.8～32 hour, is particularly preferably 1～24 hour;
Preferably, described pulverizing is for grinding;
Preferably, described compressing for adopting tablet press machine to be compressed to sheet, particularly preferably adopt tablet press machine to be compressed to the sheet that thickness is 0.2～1cm;
Preferably, described compressing pressure is 5～35Mpa, and more preferably 8～25Mpa, be particularly preferably 10～20Mpa.
9. as the described method of claim 4-8 any one, it is characterized in that, described sintering carries out in Muffle furnace;
Preferably, described programming rate be 15 ℃/below min, more preferably 0.1～10 ℃/min, be particularly preferably 1～5 ℃/min;
Preferably, described sintering temperature is 450～750 ℃, is particularly preferably 500～680 ℃;
Preferably, described coolingly carry out under cold dry air;
Preferably, describedly pulverize and sieve after cooling, then particularly preferably cooling rear grinding crosses 200 mesh sieves; Preferably, agate mortar is adopted in described grinding;
Preferably, described grind successively after cooling and dry; Preferably, described drying is vacuumize.
10. as the described method of claim 4-9 any one, it is characterized in that, described method comprises:
(1) with after lithium source, vanadium source, the abundant mixed grinding in zirconium source and yttrium source, add ball-milling medium, after ball milling under 5～120 ℃ drying 0.5h at least, then be pressed into disk;
(2) disk after suppressing is heated to 400～900 ℃ of sintering, after furnace temperature rises to 400～900 ℃, is placed in cold dry air and quenches, and grinds, and crosses 200 purposes sieves, and then vacuumize obtains lithium vanadate anode material.
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| CN110294494A (en) * | 2019-07-25 | 2019-10-01 | 哈尔滨工业大学 | Lithium vanadate anode mends lithium additive and its application |
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