CN100546076C - Method for synthesizing nano-scale lithium ion power battery cathode material by micro-reactor spontaneous combustion method - Google Patents
Method for synthesizing nano-scale lithium ion power battery cathode material by micro-reactor spontaneous combustion method Download PDFInfo
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- CN100546076C CN100546076C CNB2007101919155A CN200710191915A CN100546076C CN 100546076 C CN100546076 C CN 100546076C CN B2007101919155 A CNB2007101919155 A CN B2007101919155A CN 200710191915 A CN200710191915 A CN 200710191915A CN 100546076 C CN100546076 C CN 100546076C
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000010406 cathode material Substances 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- 230000002269 spontaneous effect Effects 0.000 title claims description 10
- 238000009841 combustion method Methods 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 238000002485 combustion reaction Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229920000742 Cotton Polymers 0.000 claims abstract description 9
- 239000002671 adjuvant Substances 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 39
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000004471 Glycine Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000006182 cathode active material Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000000843 powder Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910007052 Li—Ti—O Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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)
Abstract
The invention provides a method for synthesizing a nano-scale lithium ion power battery cathode material by utilizing self-ignition of a microreactor. The present invention uses nanometer powder of soluble metal salt or its compound as raw material, and mixes them according to the stoichiometric proportion of the material, then adds a certain quantity of combustion adjuvant, and dissolves it in water to form solution or uniformly dispersed emulsion, and uses fibrous cotton or paper to completely absorb the solution or emulsion, and makes it self-ignite to obtain precursor, then the precursor is sintered in furnace so as to obtain the invented cathode material. The method has the advantages of simple process, greatly shortened reaction time, reduced sintering temperature, environmental friendliness, suitability for large-scale production, high crystallinity of the material due to instantaneous combustion, no loss of lithium ions, small particle size of the prepared powder, uniform particle size and element distribution, improved material performance, and suitability for use as a power battery.
Description
Technical field
The present invention relates to a kind of method, belong to the lithium ion battery material technical field by microreactor burning synthesizing nano-scale lithium ion power cell cathode material.
Background technology
Lithium ion battery is the latest generation secondary cell that grows up the nineties in 20th century, and the research and development of new type lithium ion electrokinetic cell are current people's active demand, also is of great practical significance to solving global energy problem in short supply.The Li of Li-Ti-O ternary system compound-material, particularly nLi/nTi=4/5
4Ti
5O
12Material and modification thereof are the research focuses of present cathode material of lithium-ion power battery, and it has suitable discharge potential, stable cycle life, and characteristics such as cost is low, performance is good, environmentally friendly.This has just determined it not only can be applied to our the daily mobile communications tool that contacts, and also may become the electrical source of power of the vehicles that now just developing rapidly.
Negative active core-shell material spinel-type Li
4Ti
5O
12More and more be subjected to lithium battery researcher's attention with its electrochemistry superior function with special atom arrangement and uniqueness.Li
4Ti
5O
12Negative material is called " zero strain material " again, and the insertion of lithium ion and taking off insert to be to carry out the Li of generation by the coexistence of two-phase in the charge and discharge process
7Ti
5O
12Cell parameter a change very for a short time, only be increased to 0.837nm from 0.836nm, change the lava phase mutually into from spinelle, thereby improve the cycle performance and the useful life of electrode, reduced to increase and brought specific capacitance significantly to decay with cycle-index.At present synthetic Li
4Ti
5O
12And material modified method mainly contains high-temperature solid phase reaction method, electrochemical reaction method and sol-gal process etc.But these methods all exist respectively the reaction time long, temperature is high, energy consumption is big, product granularity and element skewness, shortcomings such as complex manufacturing process.Adopt the synthetic Li of microreactor spontaneous combustion method
4Ti
5O
12Lithium ion battery negative material does not appear in the newspapers.
Summary of the invention
The objective of the invention is to provide a kind of new method of low-cost low energy consumption synthesized high-performance cathode material of lithium-ion power battery.
The object of the invention technical scheme is: a kind of method by microreactor burning synthesizing nano-scale lithium ion power cell cathode material, its concrete steps are: (1) gets the soluble compound of Li, the soluble compound of Ti or nano titanium oxide, the soluble compound of metal M, according to target product molecular formula Li
wM
xTi
yO
zThe atom number ratio of middle metallic element is prepared burden, and the adding combustion adjuvant gets mixed solution or homodisperse emulsion, wherein 0＜w≤8; 0≤x＜5; 0＜y≤6; 1≤z≤12; 1/2≤w: y≤2, metal M are at least a kind of among Mg, Al, Fe, Ni, Cr, Ga, the Ag; (2) get cellulosic cotton or stationery above-mentioned mixed solution or homodisperse emulsion are all absorbed, and put into baking oven, make its spontaneous combustion; (3) with the presoma after the spontaneous combustion at aerobic or inert atmosphere sintering, can make the nano-scale lithium ion power cell cathode active material.
The soluble compound of wherein said Li is lithium nitrate, lithium carbonate, lithium chloride, lithium acetate; Or contain organic alcohol, acid or the ester type compound of lithium.The soluble compound of described Ti is titanium tetrachloride, tetrabutyl titanate; Or organic alcohol, acid, the ester type compound of titaniferous.The soluble compound of described metal M is nitrate, carbonate, chloride, the acetate of containing metal M; Or organic alcohol, acid, the ester type compound of containing metal M.Described combustion adjuvant is to be at least a kind of in the combustion adjuvants such as glycine, ammonium nitrate, urea.
The amount of substance that combustion adjuvant adds in above-mentioned preparation process is 1-4 a times of all metallic element amount of substance sums in the target product; The addition of cellulosic cotton or stationery is got 0.5-5g for every 0.01mol metallic element in the product according to target.
Autoignition temperature is 150-300 ℃ in the above-mentioned steps (2); Sintering temperature is 500-800 ℃ in the step (3), temperature retention time 4-6 hour; The sintering heating rate is controlled to be 100-200 ℃/hour.
Beneficial effect:
The used raw material of the present invention is common raw material, equipment is simple, synthesising reacting time is short, the low loss of having avoided Li of sintering temperature, manufacturing cost cheapness, and method for making is simple, meet environmental requirement, products therefrom crystallization degree height, granularity is minimum, element is evenly distributed, and has shown heavy-current discharge performance preferably.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1 product.
Fig. 2 is the first charge-discharge curve chart of the embodiment of the invention 1 product.
Fig. 3 is the different multiplying stable discharging specific capacitance curve chart of the embodiment of the invention 1 product.
Fig. 4 is 50 cyclic curve figure of heavy-current discharge of the embodiment of the invention 1 product.
Fig. 5 is the XRD figure of the embodiment of the invention 2 products.
Fig. 6 is the first charge-discharge curve chart of the embodiment of the invention 2 products.
Fig. 7 is 100 cyclic curve figure of heavy-current discharge of the embodiment of the invention 2 products.
Embodiment
Embodiment one: 0.005mol Li
4Ti
5O
12Synthetic, structural stability test and be assembled into the electrochemical property test of simulated battery with Li.
0.005mol Li at first
4Ti
5O
12In contain 0.025mol Ti, therefore the content according to Ti weighs 8.51g tetrabutyl titanate (analyzing pure), and it is dissolved in hydrolysis 20min in the distilled water, precipitation occurs, adds a small amount of nitric acid again the precipitation after the hydrolysis is dissolved, afterwards according to Li
4Ti
5O
12The ratio of the amount of middle metallics weighs 1.38g LiNO
3(analyzing pure) and 6.76g glycine all are dissolved in it in beaker that fills titanium salt.Taking by weighing 6.75g absorbent cotton at last all absorbs solution.The absorbent cotton that has absorbed solution is put into 250 ℃ in baking oven makes its spontaneous combustion obtain presoma, at last with presoma at 700 ℃ of roasting 5h, promptly get required Li
4Ti
5O
12The XRD powder diffraction method is measured and is shown the spinel structure that has formed pure phase, is illustrated in figure 1 as Li
4Ti
5O
12The XRD phase structure.As can be seen from Figure 1, the equal and Li of the position of each diffraction maximum of XRD figure of synthetic product and relative intensity
4Ti
5O
12Standard JCPDS card (26-1198) matches, and shows that product is single-phase spinel-type Li
4Ti
5O
12Lithium ion battery negative material, Li
4Ti
5O
12Crystallization degree very high.From figure, can calculate synthetic product Li
4Ti
5O
12The average grain diameter of primary particle is 34.61nm.
With the sample that makes, SuperP, LA132 press mass ratio and evenly mix at 85: 10: 5, are coated on the Copper Foil of 10 μ m thickness.Beat sheet and be placed on 100 ℃ of oven dry down of vacuum drying chamber, obtain electrode slice.With metal lithium sheet is to electrode, and electrolyte adopts 1mol/L LiPF
6, in the glove box of argon shield, be assembled into simulated battery.On the high accuracy battery tester, investigate and charge and discharge the electrode cycle performance.The 1C first charge-discharge curve that records as shown in Figure 2, synthetic product and Li are assembled into simulated battery, the 1C specific capacitance that discharges first can reach theoretical capacity 175mAh/g, charge and discharge platform is straight, visible material has good embedding lithium performance.Fig. 3 explanation: synthetic product Li
4Ti
5O
12Negative material and Li are assembled into simulated battery considerable capacity when big current stabilization discharges and recharges.10C stablizes reversible capability of charging and discharging and reaches 120mAh/g; 20C stablizes reversible capability of charging and discharging and reaches 110mAh/g; The 40C reversible capability of charging and discharging still has 75mAh/g.At the high current charge-discharge test curve as shown in Figure 4, this sample shows excellent cycle performance in the high current charge-discharge test process as can be seen, is to do the good electrode material of electrokinetic cell.
Embodiment two: 0.005mol Li
4Al
0.15Ti
4.85O
12Synthetic, structural stability test and be assembled into the electrochemical property test of simulated battery with Li.
According to the synthetic Li of the method for embodiment one
4Al
0.15Ti
4.85O
12At first the content according to Ti weighs 8.25g tetrabutyl titanate (analyzing pure), and it is dissolved in hydrolysis 20min in the distilled water, precipitation occurs, adds the precipitation dissolving after a small amount of nitric acid makes hydrolysis again, afterwards according to Li
4Al
0.15Ti
4.85O
12The ratio of the amount of middle metallics quantitatively weighs Al (NO
3)
3(analyzing pure) 0.16g and LiNO
3(analyzing pure) 13.79g is also equally according to Li
4Al
0.15Ti
4.85O
12The content of middle metal takes by weighing the 6.76g glycine and adds in the lump in the beaker that fills titanium salt.Taking by weighing 6.75g absorbent cotton at last all absorbs solution.The absorbent cotton that has absorbed solution is put into 250 ℃ in baking oven makes its spontaneous combustion obtain presoma, at last with presoma at 700 ℃ of roasting 5h, promptly get required Li
4Al
0.15Ti
4.85O
12
Li
4Al
0.15Ti
4.85O
12After powder preparing is finished, measure pattern with the XRD powder diffraction method.Be illustrated in figure 5 as Li
4Al
0.15Ti
4.85O
12The XRD phase structure, the position of each diffraction maximum of XRD figure of synthetic product and relative intensity are all and Li
4Ti
5O
12Standard JCPDS card (26-1198) matches, and has as can be seen from the figure formed the spinel structure of pure phase, and after the doped with Al, still can form and Li
4Ti
5O
12The same spinel structure, crystallization degree is very high.
With the sample that makes, be assembled into simulated battery according to method and the Li of embodiment one, on the high accuracy battery tester, investigate and charge and discharge the electrode cycle performance.The 1C first charge-discharge curve that records as shown in Figure 6, the specific capacitance that discharges first reaches theoretical capacity 175mAh/g, charge and discharge platform is straight, visible material has good embedding lithium performance.At 100 loop test curves of high current charge-discharge as shown in Figure 7, this sample shows excellent cycle performance in the high current charge-discharge test process as can be seen, and because the doping of Al, conductivity improves; Synthetic product Li
4Al
0.15Ti
4.85O
12Negative material is assembled into 100 circulation backs of simulated battery 2C with Li, all less than reducing, efficiency for charge-discharge all can reach 100% to the 10C rate charge-discharge ninety-nine times out of a hundred than discharge capacity.As seen after the doped with Al, electric conductivity improves.
Embodiment three～embodiment six:
| Raw material | Proportioning | Combustion adjuvant | Sintering temperature ℃ | Heating rate (℃/h) | |
| Embodiment three | LiNO 31.379g +TiCl 47.747g +AgNO 30.19g | Li 4Ti 5O 12/Ag(5wt.％) | Glycine 8g | 600 | 100 |
| Embodiment four | Li 2CO 30.74g+ tetrabutyl titanate 6.81g+Fe (NO 3) 31.2093g | LiFeTiO 3 | Ammonium nitrate 3g+glycine 5g | 700 | 140 |
| Embodiment five | CH 3COOLi1.287g+ tetrabutyl titanate 8.679g+Ni (NO 3) 2·6H 2O0.218g +Cr(NO 3) 30.179g | Li 1.3[CrNi] 0.1Ti 1.7O 4 | Urea 9g | 750 | 180 |
| Embodiment six | LiNO 31.379g+ sharp titanium nano-TiO 21.997g | Li 4Ti 5O 12 | Glycine 10g | 800 | 200 |
Can obtain the spinel-type negative active core-shell material of 0.005mol correspondence respectively with reference to the method for embodiment 1 or example 2 by above experiment parameter.
Claims (6)
1, a kind of method by microreactor burning synthesizing nano-scale lithium ion power cell cathode material, its concrete steps are: (1) gets the soluble compound of Li, the soluble compound of Ti or nano titanium oxide, the soluble compound of metal M, according to target product molecular formula Li
wM
xTi
yO
zThe atom number ratio of middle metallic element is prepared burden, and adds combustion adjuvant, obtains mixed solution or homodisperse emulsion, wherein 0＜w≤8; 0≤x＜5; 0＜y≤6; 1≤z≤12; 1/2≤w: y≤2, metal M are at least a kind of among Mg, Al, Fe, Ni, Cr, Ga, the Ag; (2) get cellulosic cotton or stationery above-mentioned mixed solution or homodisperse emulsion are all absorbed, and put into baking oven, make its spontaneous combustion; (3) with the presoma after the spontaneous combustion at aerobic or inert atmosphere sintering, make the nano-scale lithium ion power cell cathode active material; The temperature that wherein makes its spontaneous combustion is 150-300 ℃; Sintering temperature is 500-800 ℃, temperature retention time 4-6 hour; The sintering heating rate is controlled to be 100-200 ℃/hour.
2, method according to claim 1, the soluble compound that it is characterized in that described Li is lithium nitrate, lithium carbonate, lithium chloride or lithium acetate.
3, method according to claim 1, the soluble compound that it is characterized in that described Ti is titanium tetrachloride or tetrabutyl titanate.
4, method according to claim 1, the soluble compound that it is characterized in that described metal M are nitrate, carbonate, chloride or the acetate of containing metal M.
5, method according to claim 1 is characterized in that described combustion adjuvant is at least a kind of in glycine, ammonium nitrate or the urea.
6, method according to claim 1, the amount of substance that it is characterized in that described combustion adjuvant adding are 1-4 times of all metallic element amount of substance sums in the target product; The addition of cellulosic cotton or stationery is got 0.5-5g for every 0.01mol metallic element in the product according to target.
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| CN102068993A (en) * | 2010-11-17 | 2011-05-25 | 昆明理工大学 | Method for preparing metallic oxide catalyst by using urea combustion-supporting method |
| CN102306787A (en) * | 2011-08-01 | 2012-01-04 | 珠海锂源动力科技有限公司 | Lithium ion battery with lithium titanate and ferrous phosphate system and manufacturing method thereof |
| CN102299370B (en) * | 2011-08-12 | 2014-05-28 | 珠海锂源新能源科技有限公司 | Lithium ion power cell and preparation method thereof |
| CN102299372B (en) * | 2011-08-12 | 2014-04-23 | 珠海锂源新能源科技有限公司 | Lithium ion power battery and preparation method thereof |
| CN102299371B (en) * | 2011-08-12 | 2014-09-24 | 珠海锂源新能源科技有限公司 | Lithium ion power cell and preparation method of lithium ion power cell |
| CN102299374B (en) * | 2011-08-12 | 2014-04-23 | 珠海锂源新能源科技有限公司 | Lithium ion power battery and preparation method for lithium ion power battery |
| CN106602056A (en) * | 2016-12-30 | 2017-04-26 | 绍兴文理学院 | Lithium-rich positive electrode material and preparation method therefor |
| CN118084854B (en) * | 2024-04-23 | 2024-08-20 | 山东高密高源化工有限公司 | Preparation method of chloroethylene carbonate |
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| Title |
|---|
| Influence of various complex agents oneletrochemicalproperty of Li4Ti5O12 anode material. Yan-Jing Hao, Qiong-Yu Lai, Ji-Zheng Lu,Dong-Qiang Liu,Xiao-Yang Ji.Journal of Alloys and Compounds,Vol.439 . 2006 |
| Influence of various complex agents oneletrochemicalproperty of Li4Ti5O12 anode material. Yan-Jing Hao, Qiong-Yu Lai, Ji-Zheng Lu,Dong-Qiang Liu,Xiao-Yang Ji.Journal of Alloys and Compounds,Vol.439. 2006 * |
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