CN103022462B - 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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- CN103022462B CN103022462B CN201210557916.8A CN201210557916A CN103022462B CN 103022462 B CN103022462 B CN 103022462B CN 201210557916 A CN201210557916 A CN 201210557916A CN 103022462 B CN103022462 B CN 103022462B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 116
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 112
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 41
- 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 29
- 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
- 239000011268 mixed slurry Substances 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 25
- 239000011812 mixed powder Substances 0.000 claims description 24
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 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
- 150000001722 carbon compounds Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000001816 cooling Methods 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
- 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
- 238000005507 spraying 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 13
- 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
- 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
- 238000002156 mixing 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
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 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
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation 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
- 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
- 230000008901 benefit 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
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 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
- 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
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009818 secondary granulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
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 high-conductivity lithium titanate cathode material of lithium battery, belong to technical field of lithium ion battery negative.
Background technology
Lithium ion battery is a kind of Novel rechargeable battery grown up since nearly ten years, because it has high-energy-density, long-life, memory-less effect, the performance characteristics 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 by replace gradually traditional life-span short, to the lead-acid battery of environment and ickel-cadmium cell.
The lithium ion battery generally used now adopts material with carbon element as negative material mostly, and wherein graphite makes one with the most use.But the lithium ion diffusion coefficient of graphite material is lower, is difficult to quick charge and discharge; And the current potential of its intercalation potential and lithium metal is close, easily causes lithium metal to be separated out during over-charging of battery and produce Li dendrite, cause battery short circuit; In addition, in electrode, the insertion of lithium ion will cause change in volume, easily cause the loose of electrode and peel off.
In recent years, find can use safely and cyclical stability good lithium ion battery negative material time, spinel lithium titanate is because the performance that each side is given prominence to becomes the focus of research.In the insertion and deintercalation process of lithium ion, spinel lithium titanate structure does not almost change, and is called as " zero strain " electrode material, and repeatedly charge-discharge performance is excellent.The intercalation potential of lithium titanate is higher, not easily causes the precipitation of lithium metal, and can use in the electrolytical burning voltage interval of most liquid and avoid electrolyte decomposition or produce diaphragm, fail safe comparatively graphite improves greatly.In addition, lithium titanate discharging voltage balance, coulombic efficiency is close to 100%, and lithium ion diffusion coefficient exceeds an order of magnitude than common graphite, raw materials abundance.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 is used as negative material a lot of advantage, its application at present is still subject to the restriction of its extremely low this factor of intrinsic conductivity, so the conductivity improving lithium titanate is the key making this material break away from application bottleneck.Usually three class methods are had to improve the electric conductivity of lithium titanate: carbon doping, coated; Doped with metal elements; Prepare nano lithium titanate.Wherein carbon is coated is exactly make the thermal decomposition of carbon containing additive, serves as conducting medium at lithium titanate particle Dispersion on surface or the good carbon of coating conducting.The carbon source of usual employing has native graphite, acetylene black and carbon containing organic compound etc.
Current domestic lithium titanate preparation method many employings solid sintering technology, 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 adopts solid phase method to prepare.By anatase titanium dioxide TiO
2and Li
2cO
3, LiNO
3, one mixing in LiOH, add appropriate organic substance and carry out ball milling mixing, then first at 400-500 DEG C, be incubated 4-20h, then after at 600-750 DEG C, carry out preroast 5-20h, finally at 800-900 DEG C, carry out after baking 5-20h, after cooling, namely obtain sub-micron Li
4ti
5o
12electrode material.This preparation method's device therefor is simple, and process conditions are convenient and easy, is applicable to large-scale production.The sub-micron Li that the present invention obtains
4ti
5o
12material particle size distribution is concentrated, 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: first by anatase titanium dioxide, lithium carbonate, coated organic carbon source, adulterate and mix pulverizing by inorganic carbon source after, under nitrogen protection, carry out the 1st calcining, calcining heat is 550-650 DEG C, calcination time is 2-20 hour, obtains pre-burning product; Then after above-mentioned pre-burning product mechanical mixture being pulverized; under nitrogen protection, then carry out the 2nd high-temperature calcination, calcining heat is 700-900 DEG C; calcination time is 2-30 hour, will cross the lithium titanate that 200 mesh sieves obtain carbon modification after products therefrom mechanical crushing after calcining.The invention has the beneficial effects as follows the cycle performance and 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 sections of patent documents all adopts double-sinter process, after pre-burning, raw material is taken out ball milling again, this preparation method heats up, the process heated up again of lowering the temperature adds energy consumption, meticulous lithium carbonate material causes compacted density too little simultaneously, little can the causing again of compacted density causes in 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, provide a kind of preparation method of high-conductivity lithium titanate cathode material of lithium battery, the present invention is based on solid sintering technology, based on the principle reducing costs, be easy to business application, the lithium titanate material of high conductivity can be prepared.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
A preparation method for high-conductivity lithium titanate cathode material of lithium battery, is characterized in that: comprise following processing step:
A, take lithium-containing compound respectively in lithium ion and the titanium ion mol ratio ratio that is Li:Ti=0.8-0.85:1 and titanium-containing oxide is inserted in ball grinder, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
B, mixed slurry steps A obtained, be delivered to spray dryer and carry out granulating and drying, obtains dry presoma powder;
C, the presoma powder obtained by step B put into high temperature kiln roasting, first according to the programming rate of 1-10 DEG C/min, are elevated to 450-650 DEG C from room temperature, and keep 4-10 hour; Then according to the programming rate of 1-10 DEG C/min, temperature is elevated to 750-950 DEG C, and keeps 4-10 hour; Last cooling naturally, 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 the spinel type lithium titanate that obtains in step C and carbon compound is inserted in ball grinder, and adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
E, the mixed slurry obtained by step D, be delivered to spray dryer and carry out granulating and drying, obtains dry mixed powder;
F, the mixed powder of drying step e obtained put into high temperature kiln roasting; under inert gas shielding, according to the programming rate of 1-10 DEG C/min, be elevated to 200-400 DEG C from room temperature; and keep 2-6 hour, obtain the spinel type lithium titanate material Li coated by carbon with high conductivity
4ti
5o
12/ C and product high-conductivity lithium titanate cathode material of lithium battery 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: spraying dry inlet temperature is 150-250 DEG C, and outlet temperature is 100-150 DEG C, and charging rate is 0.01-1L/min.
Preferably, the present invention in step, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
Preferably, the present invention in step, described titanium-containing oxide be in rutile titanium dioxide, 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, wood sugar one or several arbitrarily than mixture.
Preferably, the present invention in step F, described inert gas comprise in helium, argon gas, nitrogen one or several arbitrarily than mixture.
The Advantageous Effects that the present invention brings:
1, the present invention first prepares pure spinel type lithium titanate, can obtain better lithium titanate crystal, then carries out the coated conductivity improving lithium titanate material of carbon in the later stage;
2, the present invention adopts solid sintering technology with low cost, and be easy to business application, lithium titanate material initial charge specific capacity under 1C (1C=175mA/g) multiplying power of production can reach 160mAh/g, can remain on more than 95% through 500 circulation volumes;
3, the present invention uses spraying dry to carry out granulating and drying to raw material mixed slurry, can carry out secondary granulation to nano raw material, improves follow-up roasting efficiency, and improves the compacted density of lithium titanate material;
What 4, the present invention adopted is consecutive production process, has lacked the step that middle one-step cooling heats again, has reduced energy consumption;
5, the ball milling preferred parameter that the present invention adopts ensure that the effect of mixing dispersion, 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 outcome.
Accompanying drawing explanation
Fig. 1 is high-conductivity lithium titanate cathode material of lithium battery 1C multiplying power first charge-discharge curve of the present invention;
Fig. 2 is high-conductivity lithium titanate cathode material of lithium battery 1C multiplying power of the present invention 500 cycle charge-discharge curves.
Embodiment
embodiment 1
A preparation method for high-conductivity lithium titanate cathode material of lithium battery, comprises following processing step:
A, take lithium-containing compound respectively in lithium ion and the titanium ion mol ratio ratio that is Li:Ti=0.8:1 and titanium-containing oxide is inserted in ball grinder, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
B, mixed slurry steps A obtained, be delivered to spray dryer and carry out granulating and drying, obtains dry presoma powder;
C, the presoma powder obtained by step B put into high temperature kiln roasting, first according to the programming rate of 1 DEG C/min, be elevated to 450 DEG C, and keep 4 hours from room temperature; Then according to the programming rate of 1 DEG C/min, temperature is elevated to 750 DEG C, and keeps 4 hours; Last cooling naturally, 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 the spinel type lithium titanate that obtains in step C and carbon compound is inserted in ball grinder, and adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
E, the mixed slurry obtained by step D, be delivered to spray dryer and carry out granulating and drying, obtains dry mixed powder;
F, the mixed powder of drying step e obtained put into high temperature kiln roasting; under inert gas shielding, according to the programming rate of 1 DEG C/min, be elevated to 200 DEG C from room temperature; and keep 2 hours, obtain the spinel type lithium titanate material Li coated by carbon with high conductivity
4ti
5o
12/ C and product high-conductivity lithium titanate cathode material of lithium battery of the present invention.
embodiment 2
A preparation method for high-conductivity lithium titanate cathode material of lithium battery, comprises following processing step:
A, take lithium-containing compound respectively in lithium ion and the titanium ion mol ratio ratio that is Li:Ti=0.85:1 and titanium-containing oxide is inserted in ball grinder, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
B, mixed slurry steps A obtained, be delivered to spray dryer and carry out granulating and drying, obtains dry presoma powder;
C, the presoma powder obtained by step B put into high temperature kiln roasting, first according to the programming rate of 10 DEG C/min, be elevated to 650 DEG C, and keep 10 hours from room temperature; Then according to the programming rate of 10 DEG C/min, temperature is elevated to 950 DEG C, and keeps 10 hours; Last cooling naturally, 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 the spinel type lithium titanate that obtains in step C and carbon compound is inserted in ball grinder, and adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
E, the mixed slurry obtained by step D, be delivered to spray dryer and carry out granulating and drying, obtains dry mixed powder;
F, the mixed powder of drying step e obtained put into high temperature kiln roasting; under inert gas shielding, according to the programming rate of 10 DEG C/min, be elevated to 400 DEG C from room temperature; and keep 6 hours, obtain the spinel type lithium titanate material Li coated by carbon with high conductivity
4ti
5o
12/ C and product high-conductivity lithium titanate cathode material of lithium battery of the present invention.
embodiment 3
A preparation method for high-conductivity lithium titanate cathode material of lithium battery, comprises following processing step:
A, take lithium-containing compound respectively in lithium ion and the titanium ion mol ratio ratio that is Li:Ti=0.82:1 and titanium-containing oxide is inserted in ball grinder, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
B, mixed slurry steps A obtained, be delivered to spray dryer and carry out granulating and drying, obtains dry presoma powder;
C, the presoma powder obtained by step B put into high temperature kiln roasting, first according to the programming rate of 5.5 DEG C/min, be elevated to 550 DEG C, and keep 7 hours from room temperature; Then according to the programming rate of 5.5 DEG C/min, temperature is elevated to 850 DEG C, and keeps 7 hours; Last cooling naturally, 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 the spinel type lithium titanate that obtains in step C and carbon compound is inserted in ball grinder, and adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
E, the mixed slurry obtained by step D, be delivered to spray dryer and carry out granulating and drying, obtains dry mixed powder;
F, the mixed powder of drying step e obtained put into high temperature kiln roasting; under inert gas shielding, according to the programming rate of 5.5 DEG C/min, be elevated to 300 DEG C from room temperature; and keep 4 hours, obtain the spinel type lithium titanate material Li coated by carbon with high conductivity
4ti
5o
12/ C and product high-conductivity lithium titanate cathode material of lithium battery of the present invention.
embodiment 4
A preparation method for high-conductivity lithium titanate cathode material of lithium battery, comprises following processing step:
A, take lithium-containing compound respectively in lithium ion and the titanium ion mol ratio ratio that is Li:Ti=0.84:1 and titanium-containing oxide is inserted in ball grinder, adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
B, mixed slurry steps A obtained, be delivered to spray dryer and carry out granulating and drying, obtains dry presoma powder;
C, the presoma powder obtained by step B put into high temperature kiln roasting, first according to the programming rate of 8 DEG C/min, be elevated to 620 DEG C, and keep 5 hours from room temperature; Then according to the programming rate of 3 DEG C/min, temperature is elevated to 770 DEG C, and keeps 8.5 hours; Last cooling naturally, 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 the spinel type lithium titanate that obtains in step C and carbon compound is inserted in ball grinder, and adding deionized water is dispersant, carries out ball milling, obtains the mixed slurry mixed;
E, the mixed slurry obtained by step D, be delivered to spray dryer and carry out granulating and drying, obtains dry mixed powder;
F, the mixed powder of drying step e obtained put into high temperature kiln roasting; under inert gas shielding, according to the programming rate of 6.5 DEG C/min, be elevated to 380 DEG C from room temperature; and keep 3.5 hours, obtain the spinel type lithium titanate material Li coated by carbon with high conductivity
4ti
5o
12/ C and product high-conductivity lithium titanate cathode material of lithium battery 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: spraying dry inlet temperature is 150 DEG C, and outlet temperature is 100 DEG C, and charging rate is 0.01L/min.
In step, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
In step, described titanium-containing oxide be in rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, 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: spraying dry inlet temperature is 250 DEG C, and outlet temperature is 150 DEG C, and charging rate is 1L/min.
In step, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
In step, described titanium-containing oxide be in rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, 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: spraying dry inlet temperature is 200 DEG C, and outlet temperature is 125 DEG C, and charging rate is 0.5L/min.
In step, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
In step, described titanium-containing oxide be in rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, 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: spraying dry inlet temperature is 165 DEG C, and outlet temperature is 130 DEG C, and charging rate is 0.08L/min.
In step, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
In step, described titanium-containing oxide be in rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
In step D, described carbon compound comprise in starch, fructose, glucose, sucrose, wood sugar one or several arbitrarily than mixture.
In step F, described inert gas comprise in helium, argon gas, nitrogen one or several arbitrarily than mixture.
embodiment 9
Take 0.1mol Li
2cO
3with 0.25mol Detitanium-ore-type TiO
2, inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 8 hours.By mixed slurry with the speed of 0.02L/min input spray dryer, inlet temperature is 160 DEG C, and outlet temperature is 100 DEG C, obtains dry mixed powder.The presoma powder of granulating and drying is put into high temperature kiln roasting, first according to the programming rate of 3 DEG C/min, is elevated to 600 DEG C from room temperature, and keeps 5 hours; Then according to the programming rate of 3 DEG C/min, temperature is elevated to 800 DEG C, and keeps 6 hours; Finally naturally cool with stove, obtain pure spinel-type Li
4ti
5o
12material.Take 0.001mol glucose and Li
4ti
5o
12inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 6 hours.By mixed slurry with the speed of 0.05L/min input spray dryer, inlet temperature is 200 DEG C, and outlet temperature is 120 DEG C, obtains dry mixed powder.Mixed powder is put into high temperature kiln roasting, use argon gas as protective gas, according to the programming rate of 2 DEG C/min, be elevated to 225 DEG C from room temperature, and keep 3 hours; The coated lithium titanate material Li of carbon is obtained with after stove cooling
4ti
5o
12/ C.
embodiment 10
Take 0.41mol LiOH and 0.5mol Detitanium-ore-type TiO
2, inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 8 hours.By mixed slurry with the speed of 0.4L/min input spray dryer, inlet temperature is 200 DEG C, and outlet temperature is 110 DEG C, obtains dry mixed powder.The presoma powder of granulating and drying is put into high temperature kiln roasting, first according to the programming rate of 5 DEG C/min, is elevated to 625 DEG C from room temperature, and keeps 4 hours; Then according to the programming rate of 6 DEG C/min, temperature is elevated to 900 DEG C, and keeps 5 hours; Finally naturally cool with stove, obtain pure spinel-type Li
4ti
5o
12material.Take 0.002mol starch and Li
4ti
5o
12inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 10 hours.By mixed slurry with the speed of 0.5L/min input spray dryer, inlet temperature is 180 DEG C, and outlet temperature is 120 DEG C, obtains dry mixed powder.Mixed powder is put into high temperature kiln roasting, use nitrogen as protective gas, according to the programming rate of 3 DEG C/min, be elevated to 300 DEG C from room temperature, and keep 3 hours; The coated lithium titanate material Li of carbon is obtained with after stove cooling
4ti
5o
12/ C.
embodiment 11
Take 0.62mol LiCH
3cOO and 0.75mol rutile TiO
2, inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 10 hours.By mixed slurry with the speed of 1L/min input spray dryer, inlet temperature is 180 DEG C, and outlet temperature is 140 DEG C, obtains dry mixed powder.The presoma powder of granulating and drying is put into high temperature kiln roasting, first according to the programming rate of 7 DEG C/min, is elevated to 500 DEG C from room temperature, and keeps 8 hours; Then according to the programming rate of 7 DEG C/min, temperature is elevated to 850 DEG C, and keeps 8 hours; Finally naturally cool with stove, obtain pure spinel-type Li
4ti
5o
12material.Take 0.001mol fructose and Li
4ti
5o
12inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 6 hours.By mixed slurry with the speed of 0.05L/min input spray dryer, inlet temperature is 150 DEG C, and outlet temperature is 120 DEG C, obtains dry mixed powder.Mixed powder is put into high temperature kiln roasting, use helium as protective gas, according to the programming rate of 2 DEG C/min, be elevated to 425 DEG C from room temperature, and keep 3 hours; The coated lithium titanate material Li of carbon is obtained with after stove cooling
4ti
5o
12/ C.
embodiment 12
Take 0.4 Li
2c
2o
4with 1mol Detitanium-ore-type TiO
2, inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 7 hours.By mixed slurry with the speed of 0.5L/min input spray dryer, inlet temperature is 250 DEG C, and outlet temperature is 120 DEG C, obtains dry mixed powder.The presoma powder of granulating and drying is put into high temperature kiln roasting, first according to the programming rate of 6 DEG C/min, is elevated to 550 DEG C from room temperature, and keeps 6 hours; Then according to the programming rate of 6 DEG C/min, temperature is elevated to 950 DEG C, and keeps 6 hours; Finally naturally cool with stove, obtain pure spinel-type Li
4ti
5o
12material.Take 0.002mol wood sugar and Li
4ti
5o
12inserting in ball grinder and to add deionized water as dispersant, ball milling obtains mixed slurry in 6 hours.By mixed slurry with the speed of 0.6L/min input spray dryer, inlet temperature is 180 DEG C, and outlet temperature is 100 DEG C, obtains dry mixed powder.Mixed powder is put into high temperature kiln roasting, use argon gas as protective gas, according to the programming rate of 5 DEG C/min, be elevated to 350 DEG C from room temperature, and keep 4 hours; The coated lithium titanate material Li of carbon is obtained with after stove cooling
4ti
5o
12/ C.
embodiment 13
The 8:1:1 mixing in mass ratio of electrode material embodiment 1 prepared, conductive agent conductive black and binding agent Kynoar, adds 1-methyl-2 pyrrolidones and stirs as solvent.After stirring, use coating apparatus to be evenly applied in the aluminum foil current collector that diameter is 14 mm, toast 12 hours in 80 DEG C of drying boxes, then use tablet press machine compacting evenly, obtained electrode slice to be measured.In the atmosphere glove box of oxygen content≤0.1ppm, water content≤0.1ppm, electrode slice is assembled into coin shape test battery, be wherein metal lithium sheet to electrode, barrier film is Celgard 2325 composite membrane, 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 negative material prepared by example 1 fills does constant current charge-discharge test between 1-2.5V voltage range, under 1C (1C=175mA/g) multiplying power, its first charge-discharge curve as shown in Figure 1, 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 multi-electrode material and be assembled into coin shape test battery according to method described in embodiment 13, constant current charge-discharge test is done between 1-2.5V voltage range, 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; Its charge specific capacity after 500 times that circulates is 152.5 mAh/g, and specific discharge capacity is 152.5 mAh/g, and efficiency remains on more than 95%.
embodiment 15
Embodiment 11 is prepared multi-electrode material and be assembled into coin shape test battery according to method described in embodiment 13, constant current charge-discharge test is done between 1-2.5V voltage range, 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
Electrode material embodiment 12 prepared is assembled into coin shape test battery according to method described in embodiment 13, constant current charge-discharge test is done between 1-2.5V voltage range, 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 (5)
1. a preparation method for high-conductivity lithium titanate cathode material of lithium battery, is characterized in that: comprise following processing step:
A, take lithium-containing compound respectively in lithium ion and the titanium ion mol ratio ratio that is Li:Ti=0.84:1 and titanium-containing oxide is inserted in ball grinder, adding deionized water is dispersant, carries out ball milling 9 hours, obtains the mixed slurry mixed;
B, mixed slurry steps A obtained, be delivered to spray dryer and carry out granulating and drying, obtains dry presoma powder; Spraying dry inlet temperature is 165 DEG C, and outlet temperature is 130 DEG C, and charging rate is 0.08L/min;
C, the presoma powder obtained by step B put into high temperature kiln roasting, first according to the programming rate of 8 DEG C/min, be elevated to 620 DEG C, and keep 5 hours from room temperature; Then according to the programming rate of 3 DEG C/min, temperature is elevated to 770 DEG C, and keeps 8.5 hours; Last cooling naturally, 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 the spinel type lithium titanate that obtains in step C and carbon compound is inserted in ball grinder, and adding deionized water is dispersant, carries out ball milling 9 hours, obtains the mixed slurry mixed;
E, the mixed slurry obtained by step D, be delivered to spray dryer and carry out granulating and drying, obtains dry mixed powder; Spraying dry inlet temperature is 165 DEG C, and outlet temperature is 130 DEG C, and charging rate is 0.08L/min;
F, the mixed powder of drying step e obtained put into high temperature kiln roasting; under inert gas shielding, according to the programming rate of 6.5 DEG C/min, be elevated to 380 DEG C from room temperature; and keep 3.5 hours, obtain the spinel type lithium titanate material Li coated by carbon with high conductivity
4ti
5o
12/ C and product high-conductivity lithium titanate cathode material of lithium battery of the present invention.
2. the preparation method of a kind of high-conductivity lithium titanate cathode material of lithium battery according to claim 1, it is characterized in that: in step, described lithium-containing compound be in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
3. the preparation method of a kind of high-conductivity lithium titanate cathode material of lithium battery according to claim 1, it is characterized in that: in step, described titanium-containing oxide be in rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
4. the preparation method of a kind of high-conductivity lithium titanate cathode material of lithium battery according to claim 1, it is characterized in that: in step D, described carbon compound comprise in starch, fructose, glucose, sucrose, wood sugar one or several arbitrarily than mixture.
5. the preparation method of a kind of high-conductivity lithium titanate cathode material of lithium battery according to claim 1, is characterized in that: in step F, described inert gas comprise in helium, argon gas, nitrogen one or several arbitrarily than mixture.
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