CN103022462A - Preparation method for high-conductivity lithium titanate cathode material of lithium battery - Google Patents
Preparation method for high-conductivity lithium titanate cathode material of lithium battery Download PDFInfo
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- CN103022462A CN103022462A CN2012105579168A CN201210557916A CN103022462A CN 103022462 A CN103022462 A CN 103022462A CN 2012105579168 A CN2012105579168 A CN 2012105579168A CN 201210557916 A CN201210557916 A CN 201210557916A CN 103022462 A CN103022462 A CN 103022462A
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- lithium titanate
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 122
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 118
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000010406 cathode material Substances 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 23
- 239000011029 spinel Substances 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims description 50
- 239000011268 mixed slurry Substances 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 30
- 239000011812 mixed powder Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000010405 anode material Substances 0.000 claims description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 20
- 239000007921 spray Substances 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 150000001722 carbon compounds Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- 239000005715 Fructose Substances 0.000 claims description 7
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 7
- 229930091371 Fructose Natural products 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 7
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 229960003487 xylose Drugs 0.000 claims description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- -1 carbon-modified lithium titanate Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Images
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method for a high-conductivity lithium titanate cathode material of a lithium battery, and belongs to the technical field of cathode materials of lithium ion batteries. Firstly, better lithium titanate crystals can be obtained by preparing pure spinel lithium titanate, and the conductivity of the lithium titanate material can be improved by carrying out carbon covering at a later stage; and secondly, a solid-phase sintering method with low cost is adopted for the contribution to commercial application, the initial charge specific capacity of the produced lithium titanate material at the rate of 1 C (1 C is 175 mA/g) can reach 160 mAh/g, and the capacity can keep more than 95% after 500 times of circulation.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, specifically, the present invention relates to a kind of preparation method of lithium battery high conductivity lithium titanate anode material, belong to the lithium ion battery negative material technical field.
Background technology
Lithium ion battery is a kind of novel rechargeable battery that has grown up since nearly ten years, because it has high-energy-density, long-life, memory-less effect, the characteristic of property such as pollution-free, lithium ion battery has had many application in fields such as portable electric appts, electric vehicle, electrical source of power, and will replace gradually traditional life-span short, to lead-acid battery and the ickel-cadmium cell of environment.
The lithium ion battery that generally uses now adopts material with carbon element as negative material mostly, wherein graphite be make with the most use a kind of.But the lithium ion diffusion coefficient of graphite material is lower, is difficult to charge and discharge fast; And the current potential of its embedding lithium current potential and lithium metal approaches, and easily causes lithium metal to separate out the generation Li dendrite during over-charging of battery, causes battery short circuit; In addition, the insertion of lithium ion will cause change in volume in the electrode, easily cause the loose of electrode and peel off.
In recent years, when the lithium ion battery negative material that searching can be used safely and cyclical stability is good, spinel lithium titanate is because the outstanding performance of each side becomes the focus of research.In the insertion of lithium ion with take off in the embedding process, the spinel lithium titanate structure does not almost change, and is called as " zero strain " electrode material, and repeatedly charge-discharge performance is excellent.The embedding lithium current potential of lithium titanate is higher, is difficult for causing separating out of lithium metal, can use in the electrolytical burning voltage of most liquid interval and avoids electrolyte decomposition or produce diaphragm, and fail safe improves greatly than graphite.In addition, the lithium titanate discharging voltage balance, enclosed pasture efficient is near 100%, and the lithium ion diffusion coefficient exceeds an order of magnitude than common graphite, and the raw materials source is abundant.The preparation method of lithium titanate is more, usually substantially can be divided into solid phase method and liquid phase method.Wherein solid phase method technique is simple, and cost is lower, is convenient to realize commercial Application.
Although spinel lithium titanate has a lot of advantages as negative material, at present its application still is subject to the restriction of its extremely low this factor of intrinsic conductivity, is to make this material break away from the key of using bottleneck so improve the conductivity of lithium titanate.Usually have three class methods to improve the electric conductivity of lithium titanate: carbon mixes, coats; Doped with metal elements; The preparation nano lithium titanate.Wherein the carbon coating is exactly to make the thermal decomposition of carbon containing additive, serves as conducting medium in the dispersion of lithium titanate particle surface or the good carbon of coating conducting.Usually the carbon source that adopts has native graphite, acetylene black and carbon containing organic compound etc.
Present domestic lithium titanate preparation method adopts solid sintering technology more, and is as follows:
It is 200710059624.0 that State Intellectual Property Office discloses an application number in 2008.2.6, name is called the patent of invention of " a kind of submicron secondary battery material and preparation method thereof ", this patent provides a kind of sub-micron electrodes material for lithium rechargeable battery and preparation method thereof, is intended to improve lithium rechargeable battery circulation and high rate performance.This sub-micron electrodes material is to adopt the solid phase method preparation.With anatase titanium dioxide TiO
2And Li
2CO
3, LiNO
3, a kind of mixing among the LiOH, add an amount of organic substance and carry out the ball milling mixing, then first at 400-500 ℃ of lower insulation 4-20h, the rear preroast 5-20h that under 600-750 ℃, carries out, under 800-900 ℃, carry out at last after baking 5-20h, namely get sub-micron Li after the cooling
4Ti
5O
12Electrode material.This preparation method's device therefor is simple, and process conditions are convenient and easy, is fit to large-scale production.The sub-micron Li that the present invention obtains
4Ti
5O
12Material particle size distributes and concentrates, and has good high rate performance and cycle life, is suitable as the electrode material of lithium ion battery.
It is 201010107707.4 that State Intellectual Property Office discloses an application number in 2010.7.14, name is called the patent of invention of " a kind of preparation method of carbon-modified lithium titanate ", this patent relates to a kind of preparation method of carbon-modified lithium titanate, belongs to a kind of preparation method of lithium ion battery negative material.Step of the present invention is as follows: after at first anatase titanium dioxide, lithium carbonate, coating being mixed pulverizing with organic carbon source, doping with inorganic carbon source, under nitrogen protection, carry out the 1st calcining, calcining heat is 550-650 ℃, calcination time is 2-20 hour, obtains the pre-burning product; Then after above-mentioned pre-burning product mechanical mixture being pulverized; under nitrogen protection, carry out again the 2nd high-temperature calcination, calcining heat is 700-900 ℃; calcination time is 2-30 hour, will cross the lithium titanate that 200 mesh sieves obtain the carbon modification after the products therefrom mechanical crushing after the calcining.The invention has the beneficial effects as follows cycle performance and the high rate performance that can improve lithium titanate material, and be easy to preparation, with low cost, environment friendly and pollution-free, be applicable to suitability for industrialized production.
Technical scheme in above-mentioned two pieces of patent documents all adopts double-sinter process, after pre-burning, raw material taken out again ball milling, this preparation method heats up, the process that cooling heats up has again increased energy consumption, meticulous lithium carbonate material causes compacted density too little simultaneously, little can the causing again of compacted density causes in the post-production cell process, and the active material of the battery of same size is on the low side, the problem that battery capacity is less than normal.
Summary of the invention
It is high that the present invention is intended to solve preparation method's energy consumption of the prior art, and the problem that compacted density is little, a kind of preparation method of lithium battery high conductivity lithium titanate anode material is provided, the present invention is take solid sintering technology as the basis, based on reducing cost, being easy to the commercial principle of using, can prepare the lithium titanate material of high conductivity.
In order to realize the foregoing invention purpose, its concrete technical scheme is as follows:
A kind of preparation method of lithium battery high conductivity lithium titanate anode material is characterized in that: comprise following processing step:
A, be that the ratio of Li:Ti=0.8-0.85:1 takes by weighing respectively lithium-containing compound and titanium-containing oxide is inserted in the ball grinder in lithium ion and titanium ion mol ratio, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
B, with the mixed slurry that steps A obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry presoma powder;
C, the presoma powder that step B is obtained are put into the high temperature kiln roasting, at first according to the programming rate of 1-10 ℃/min, are elevated to 450-650 ℃ from room temperature, and keep 4-10 hour; Then according to the programming rate of 1-10 ℃/min, temperature is elevated to 750-950 ℃, and keeps 4-10 hour; Last naturally cooling obtains spinel type lithium titanate material Li
4Ti
5O
12
D, be Li according to the mol ratio of lithium titanate and carbon
4Ti
5O
12: the ratio of C=1:0.001-0.01 takes by weighing the spinel type lithium titanate and the carbon compound that obtain among the step C and inserts in the ball grinder, and the adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
E, with the mixed slurry that step D obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry mixed powder;
The mixed powder of F, drying that step e is obtained is put into the high temperature kiln roasting; under inert gas shielding, according to the programming rate of 1-10 ℃/min, be elevated to 200-400 ℃ from room temperature; and kept the spinel type lithium titanate material Li by the carbon coating that obtains to have high conductivity 2-6 hour
4Ti
5O
12/ C is product lithium battery high conductivity lithium titanate anode material of the present invention.
Preferably, the present invention is in steps A and step D, and described ball milling is ball milling 6-10 hour.
Preferably, the present invention is in step B and step e, and described granulating and drying is specially: the spray drying inlet temperature is 150-250 ℃, and outlet temperature is 100-150 ℃, and charging rate is 0.01-1L/min.
Preferably, the present invention in steps A, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate one or several arbitrarily than mixture.
Preferably, the present invention in steps A, described titanium-containing oxide be in rutile titanium dioxide, the anatase titanium dioxide one or several arbitrarily than mixture.
Preferably, the present invention in step D, described carbon compound comprise in starch, fructose, glucose, sucrose, the wood sugar one or several arbitrarily than mixture.
Preferably, the present invention in step F, described inert gas comprise in helium, argon gas, the nitrogen one or several arbitrarily than mixture.
The useful technique effect that the present invention brings:
1, the present invention prepares first pure spinel type lithium titanate, can obtain better lithium titanate crystal, carries out carbon in the later stage again and coats the conductivity that can improve lithium titanate material;
2, the present invention adopts solid sintering technology with low cost, is easy to commercial the application, and the lithium titanate material of production initial charge specific capacity under 1C (1C=175mA/g) multiplying power can reach 160mAh/g, can remain on more than 95% through 500 circulation volumes;
3, the present invention uses spray drying that the raw material mixed slurry is carried out granulating and drying, can carry out secondary granulation to nano raw material, improves follow-up roasting efficient, and improves the compacted density of lithium titanate material;
What 4, the present invention adopted is the consecutive production process, and one section step that cooling is heated again in the middle of having lacked has reduced energy consumption;
5, the ball milling preferred parameter of the present invention's employing has guaranteed to mix the effect of disperseing, and mixes; The preferred spray-dired parameter that the present invention adopts can effectively make material dry rapidly in spray-drying process, and can obtain desirable granulation effect.
Description of drawings
Fig. 1 is lithium battery high conductivity lithium titanate anode material 1C multiplying power first charge-discharge curve of the present invention;
Fig. 2 is 500 cycle charge-discharge curves of lithium battery high conductivity lithium titanate anode material 1C multiplying power of the present invention.
Embodiment
Embodiment 1
A kind of preparation method of lithium battery high conductivity lithium titanate anode material comprises following processing step:
A, be that the ratio of Li:Ti=0.8:1 takes by weighing respectively lithium-containing compound and titanium-containing oxide is inserted in the ball grinder in lithium ion and titanium ion mol ratio, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
B, with the mixed slurry that steps A obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry presoma powder;
C, the presoma powder that step B is obtained are put into the high temperature kiln roasting, at first according to the programming rate of 1 ℃/min, are elevated to 450 ℃ from room temperature, and keep 4 hours; Then according to the programming rate of 1 ℃/min, temperature is elevated to 750 ℃, and keeps 4 hours; Last naturally cooling obtains spinel type lithium titanate material Li
4Ti
5O
12
D, be Li according to the mol ratio of lithium titanate and carbon
4Ti
5O
12: the ratio of C=1:0.001 takes by weighing the spinel type lithium titanate and the carbon compound that obtain among the step C and inserts in the ball grinder, and the adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
E, with the mixed slurry that step D obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry mixed powder;
The mixed powder of F, drying that step e is obtained is put into the high temperature kiln roasting; under inert gas shielding, according to the programming rate of 1 ℃/min, be elevated to 200 ℃ from room temperature; and kept 2 hours, obtain to have the spinel type lithium titanate material Li by the carbon coating of high conductivity
4Ti
5O
12/ C is product lithium battery high conductivity lithium titanate anode material of the present invention.
A kind of preparation method of lithium battery high conductivity lithium titanate anode material comprises following processing step:
A, be that the ratio of Li:Ti=0.85:1 takes by weighing respectively lithium-containing compound and titanium-containing oxide is inserted in the ball grinder in lithium ion and titanium ion mol ratio, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
B, with the mixed slurry that steps A obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry presoma powder;
C, the presoma powder that step B is obtained are put into the high temperature kiln roasting, at first according to the programming rate of 10 ℃/min, are elevated to 650 ℃ from room temperature, and keep 10 hours; Then according to the programming rate of 10 ℃/min, temperature is elevated to 950 ℃, and keeps 10 hours; Last naturally cooling obtains spinel type lithium titanate material Li
4Ti
5O
12
D, be Li according to the mol ratio of lithium titanate and carbon
4Ti
5O
12: the ratio of C=1:0.01 takes by weighing the spinel type lithium titanate and the carbon compound that obtain among the step C and inserts in the ball grinder, and the adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
E, with the mixed slurry that step D obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry mixed powder;
The mixed powder of F, drying that step e is obtained is put into the high temperature kiln roasting; under inert gas shielding, according to the programming rate of 10 ℃/min, be elevated to 400 ℃ from room temperature; and kept 6 hours, obtain to have the spinel type lithium titanate material Li by the carbon coating of high conductivity
4Ti
5O
12/ C is product lithium battery high conductivity lithium titanate anode material of the present invention.
Embodiment 3
A kind of preparation method of lithium battery high conductivity lithium titanate anode material comprises following processing step:
A, be that the ratio of Li:Ti=0.82:1 takes by weighing respectively lithium-containing compound and titanium-containing oxide is inserted in the ball grinder in lithium ion and titanium ion mol ratio, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
B, with the mixed slurry that steps A obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry presoma powder;
C, the presoma powder that step B is obtained are put into the high temperature kiln roasting, at first according to the programming rate of 5.5 ℃/min, are elevated to 550 ℃ from room temperature, and keep 7 hours; Then according to the programming rate of 5.5 ℃/min, temperature is elevated to 850 ℃, and keeps 7 hours; Last naturally cooling obtains spinel type lithium titanate material Li
4Ti
5O
12
D, be Li according to the mol ratio of lithium titanate and carbon
4Ti
5O
12: the ratio of C=1:0.005 takes by weighing the spinel type lithium titanate and the carbon compound that obtain among the step C and inserts in the ball grinder, and the adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
E, with the mixed slurry that step D obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry mixed powder;
The mixed powder of F, drying that step e is obtained is put into the high temperature kiln roasting; under inert gas shielding, according to the programming rate of 5.5 ℃/min, be elevated to 300 ℃ from room temperature; and kept 4 hours, obtain to have the spinel type lithium titanate material Li by the carbon coating of high conductivity
4Ti
5O
12/ C is product lithium battery high conductivity lithium titanate anode material of the present invention.
Embodiment 4
A kind of preparation method of lithium battery high conductivity lithium titanate anode material comprises following processing step:
A, be that the ratio of Li:Ti=0.84:1 takes by weighing respectively lithium-containing compound and titanium-containing oxide is inserted in the ball grinder in lithium ion and titanium ion mol ratio, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
B, with the mixed slurry that steps A obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry presoma powder;
C, the presoma powder that step B is obtained are put into the high temperature kiln roasting, at first according to the programming rate of 8 ℃/min, are elevated to 620 ℃ from room temperature, and keep 5 hours; Then according to the programming rate of 3 ℃/min, temperature is elevated to 770 ℃, and keeps 8.5 hours; Last naturally cooling obtains spinel type lithium titanate material Li
4Ti
5O
12
D, be Li according to the mol ratio of lithium titanate and carbon
4Ti
5O
12: the ratio of C=1:0.008 takes by weighing the spinel type lithium titanate and the carbon compound that obtain among the step C and inserts in the ball grinder, and the adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
E, with the mixed slurry that step D obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry mixed powder;
The mixed powder of F, drying that step e is obtained is put into the high temperature kiln roasting; under inert gas shielding, according to the programming rate of 6.5 ℃/min, be elevated to 380 ℃ from room temperature; and kept 3.5 hours, obtain to have the spinel type lithium titanate material Li by the carbon coating of high conductivity
4Ti
5O
12/ C is product lithium battery high conductivity lithium titanate anode material of the present invention.
Embodiment 5
On the basis of embodiment 1-4, preferred:
In steps A and step D, described ball milling is ball milling 6 hours.
In step B and step e, described granulating and drying is specially: the spray drying inlet temperature is 150 ℃, and outlet temperature is 100 ℃, and charging rate is 0.01L/min.
In steps A, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate one or several arbitrarily than mixture.
In steps A, described titanium-containing oxide be in rutile titanium dioxide, the anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, the wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, the nitrogen one or several arbitrarily than mixture.
Embodiment 6
On the basis of embodiment 1-4, preferred:
In steps A and step D, described ball milling is ball milling 10 hours.
In step B and step e, described granulating and drying is specially: the spray drying inlet temperature is 250 ℃, and outlet temperature is 150 ℃, and charging rate is 1L/min.
In steps A, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate one or several arbitrarily than mixture.
In steps A, described titanium-containing oxide be in rutile titanium dioxide, the anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, the wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, the nitrogen one or several arbitrarily than mixture.
Embodiment 7
On the basis of embodiment 1-4, preferred:
In steps A and step D, described ball milling is ball milling 8 hours.
In step B and step e, described granulating and drying is specially: the spray drying inlet temperature is 200 ℃, and outlet temperature is 125 ℃, and charging rate is 0.5L/min.
In steps A, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate one or several arbitrarily than mixture.
In steps A, described titanium-containing oxide be in rutile titanium dioxide, the anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, the wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, the nitrogen one or several arbitrarily than mixture.
Embodiment 8
On the basis of embodiment 1-4, preferred:
In steps A and step D, described ball milling is ball milling 9 hours.
In step B and step e, described granulating and drying is specially: the spray drying inlet temperature is 165 ℃, and outlet temperature is 130 ℃, and charging rate is 0.08L/min.
In steps A, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate one or several arbitrarily than mixture.
In steps A, described titanium-containing oxide be in rutile titanium dioxide, the anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, the wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, the nitrogen one or several arbitrarily than mixture.
Embodiment 9
Take by weighing 0.1mol Li
2CO
3With 0.25mol Detitanium-ore-type TiO
2, to insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 8 hours.With the speed input spray dryer of mixed slurry with 0.02L/min, inlet temperature is 160 ℃, and outlet temperature is 100 ℃, obtains dry mixed powder.The presoma powder of granulating and drying is put into the high temperature kiln roasting, at first according to the programming rate of 3 ℃/min, be elevated to 600 ℃ from room temperature, and kept 5 hours; Then according to the programming rate of 3 ℃/min, temperature is elevated to 800 ℃, and keeps 6 hours; Naturally cool off with stove at last, obtain pure spinel-type Li
4Ti
5O
12Material.Take by weighing 0.001mol glucose and Li
4Ti
5O
12Insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 6 hours.With the speed input spray dryer of mixed slurry with 0.05L/min, inlet temperature is 200 ℃, and outlet temperature is 120 ℃, obtains dry mixed powder.Mixed powder is put into the high temperature kiln roasting, use argon gas as protective gas, according to the programming rate of 2 ℃/min, be elevated to 225 ℃ from room temperature, and kept 3 hours; With obtaining the lithium titanate material Li that carbon coats after the stove cooling
4Ti
5O
12/ C.
Embodiment 10
Take by weighing 0.41mol LiOH and 0.5mol Detitanium-ore-type TiO
2, to insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 8 hours.With the speed input spray dryer of mixed slurry with 0.4L/min, inlet temperature is 200 ℃, and outlet temperature is 110 ℃, obtains dry mixed powder.The presoma powder of granulating and drying is put into the high temperature kiln roasting, at first according to the programming rate of 5 ℃/min, be elevated to 625 ℃ from room temperature, and kept 4 hours; Then according to the programming rate of 6 ℃/min, temperature is elevated to 900 ℃, and keeps 5 hours; Naturally cool off with stove at last, obtain pure spinel-type Li
4Ti
5O
12Material.Take by weighing 0.002mol starch and Li
4Ti
5O
12Insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 10 hours.With the speed input spray dryer of mixed slurry with 0.5L/min, inlet temperature is 180 ℃, and outlet temperature is 120 ℃, obtains dry mixed powder.Mixed powder is put into the high temperature kiln roasting, use nitrogen as protective gas, according to the programming rate of 3 ℃/min, be elevated to 300 ℃ from room temperature, and kept 3 hours; With obtaining the lithium titanate material Li that carbon coats after the stove cooling
4Ti
5O
12/ C.
Embodiment 11
Take by weighing 0.62mol LiCH
3COO and 0.75mol rutile TiO
2, to insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 10 hours.With the speed input spray dryer of mixed slurry with 1L/min, inlet temperature is 180 ℃, and outlet temperature is 140 ℃, obtains dry mixed powder.The presoma powder of granulating and drying is put into the high temperature kiln roasting, at first according to the programming rate of 7 ℃/min, be elevated to 500 ℃ from room temperature, and kept 8 hours; Then according to the programming rate of 7 ℃/min, temperature is elevated to 850 ℃, and keeps 8 hours; Naturally cool off with stove at last, obtain pure spinel-type Li
4Ti
5O
12Material.Take by weighing 0.001mol fructose and Li
4Ti
5O
12Insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 6 hours.With the speed input spray dryer of mixed slurry with 0.05L/min, inlet temperature is 150 ℃, and outlet temperature is 120 ℃, obtains dry mixed powder.Mixed powder is put into the high temperature kiln roasting, use helium as protective gas, according to the programming rate of 2 ℃/min, be elevated to 425 ℃ from room temperature, and kept 3 hours; With obtaining the lithium titanate material Li that carbon coats after the stove cooling
4Ti
5O
12/ C.
Embodiment 12
Take by weighing 0.4 Li
2C
2O
4With 1mol Detitanium-ore-type TiO
2, to insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 7 hours.With the speed input spray dryer of mixed slurry with 0.5L/min, inlet temperature is 250 ℃, and outlet temperature is 120 ℃, obtains dry mixed powder.The presoma powder of granulating and drying is put into the high temperature kiln roasting, at first according to the programming rate of 6 ℃/min, be elevated to 550 ℃ from room temperature, and kept 6 hours; Then according to the programming rate of 6 ℃/min, temperature is elevated to 950 ℃, and keeps 6 hours; Naturally cool off with stove at last, obtain pure spinel-type Li
4Ti
5O
12Material.Take by weighing 0.002mol wood sugar and Li
4Ti
5O
12Insert in the ball grinder and add deionized water as dispersant, ball milling obtained mixed slurry in 6 hours.With the speed input spray dryer of mixed slurry with 0.6L/min, inlet temperature is 180 ℃, and outlet temperature is 100 ℃, obtains dry mixed powder.Mixed powder is put into the high temperature kiln roasting, use argon gas as protective gas, according to the programming rate of 5 ℃/min, be elevated to 350 ℃ from room temperature, and kept 4 hours; With obtaining the lithium titanate material Li that carbon coats after the stove cooling
4Ti
5O
12/ C.
Embodiment 13
In mass ratio 8:1:1 mixing of electrode material, conductive agent conductive black and binding agent Kynoar with embodiment 1 prepares adds 1-methyl-2 pyrrolidones and stirs as solvent.After stirring, use coating apparatus evenly to be applied on the aluminum foil current collector that diameter is 14 mm, baking is 12 hours in 80 ℃ of drying boxes, then uses the tablet press machine compacting evenly, makes electrode slice to be measured.In the atmosphere glove box of oxygen content≤0.1ppm, water content≤0.1ppm, electrode slice is assembled into the coin shape test battery, be metal lithium sheet to electrode wherein, barrier film is Celgard 2325 composite membranes, and electrolyte is 1 mol/L lithium hexafluoro phosphate and the mixed solution of equal-volume than ethylene carbonate, dimethyl carbonic ether.The battery that the negative material of example 1 preparation fills is done the constant current charge-discharge test between the 1-2.5V voltage range, under 1C (1C=175mA/g) multiplying power, its first charge-discharge curve as shown in Figure 1, the initial charge specific capacity is 162.9mAh/g, first discharge specific capacity is 164.2mAh/g, and first charge-discharge efficiency is 99%.
Embodiment 14
Embodiment 10 is prepared the multi-electrode material be assembled into the coin shape test battery according to embodiment 13 described methods, between the 1-2.5V voltage range, do the constant current charge-discharge test, under 1C (1C=175mA/g) multiplying power, its initial charge specific capacity is 159.4mAh/g, and first discharge specific capacity is 158.4mAh/g; Circulating, its charge ratio capacity is 152.5 mAh/g after 500 times, and specific discharge capacity is 152.5 mAh/g, and efficient remains on more than 95%.
Embodiment 15
Embodiment 11 is prepared the multi-electrode material be assembled into the coin shape test battery according to embodiment 13 described methods, between the 1-2.5V voltage range, do the constant current charge-discharge test, under 1C (1C=175mA/g) multiplying power, its initial charge specific capacity is 162.3mAh/g, and first discharge specific capacity is 160.9mAh/g; Under 5C (1C=175mA/g) multiplying power, its initial charge specific capacity is 140.1mAh/g, and first discharge specific capacity is 138.5mAh/g.
Embodiment 16
The electrode material that embodiment 12 is prepared is assembled into the coin shape test battery according to embodiment 13 described methods, between the 1-2.5V voltage range, do the constant current charge-discharge test, under 1C (1C=175mA/g) multiplying power, its initial charge specific capacity is 161mAh/g, and first discharge specific capacity is 160.2mAh/g; Under 5C (1C=175mA/g) multiplying power, its initial charge specific capacity is 141mAh/g, and first discharge specific capacity is 137.8mAh/g.
Claims (7)
1. the preparation method of a lithium battery high conductivity lithium titanate anode material is characterized in that: comprise following processing step:
A, be that the ratio of Li:Ti=0.8-0.85:1 takes by weighing respectively lithium-containing compound and titanium-containing oxide is inserted in the ball grinder in lithium ion and titanium ion mol ratio, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
B, with the mixed slurry that steps A obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry presoma powder;
C, the presoma powder that step B is obtained are put into the high temperature kiln roasting, at first according to the programming rate of 1-10 ℃/min, are elevated to 450-650 ℃ from room temperature, and keep 4-10 hour; Then according to the programming rate of 1-10 ℃/min, temperature is elevated to 750-950 ℃, and keeps 4-10 hour; Last naturally cooling obtains spinel type lithium titanate material Li
4Ti
5O
12
D, be Li according to the mol ratio of lithium titanate and carbon
4Ti
5O
12: the ratio of C=1:0.001-0.01 takes by weighing the spinel type lithium titanate and the carbon compound that obtain among the step C and inserts in the ball grinder, and the adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry that mixes;
E, with the mixed slurry that step D obtains, be delivered to spray dryer and carry out granulating and drying, obtain dry mixed powder;
The mixed powder of F, drying that step e is obtained is put into the high temperature kiln roasting; under inert gas shielding, according to the programming rate of 1-10 ℃/min, be elevated to 200-400 ℃ from room temperature; and kept the spinel type lithium titanate material Li by the carbon coating that obtains to have high conductivity 2-6 hour
4Ti
5O
12/ C is product lithium battery high conductivity lithium titanate anode material of the present invention.
2. the preparation method of a kind of lithium battery high conductivity lithium titanate anode material according to claim 1 is characterized in that: in steps A and step D, described ball milling is ball milling 6-10 hour.
3. the preparation method of a kind of lithium battery high conductivity lithium titanate anode material according to claim 1, it is characterized in that: in step B and step e, described granulating and drying is specially: the spray drying inlet temperature is 150-250 ℃, outlet temperature is 100-150 ℃, and charging rate is 0.01-1L/min.
4. the preparation method of a kind of lithium battery high conductivity lithium titanate anode material according to claim 1, it is characterized in that: in steps A, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate one or several arbitrarily than mixture.
5. the preparation method of a kind of lithium battery high conductivity lithium titanate anode material according to claim 1, it is characterized in that: in steps A, described titanium-containing oxide be in rutile titanium dioxide, the anatase titanium dioxide one or several arbitrarily than mixture.
6. the preparation method of a kind of lithium battery high conductivity lithium titanate anode material according to claim 1, it is characterized in that: in step D, described carbon compound comprise in starch, fructose, glucose, sucrose, the wood sugar one or several arbitrarily than mixture.
7. the preparation method of a kind of lithium battery high conductivity lithium titanate anode material according to claim 1 is characterized in that: in step F, described inert gas comprise in helium, argon gas, the nitrogen one or several arbitrarily than mixture.
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