CN1744354A - Surface modifying methal forlithium ion cell cathode active material - Google Patents
Surface modifying methal forlithium ion cell cathode active material Download PDFInfo
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- CN1744354A CN1744354A CNA200510096132XA CN200510096132A CN1744354A CN 1744354 A CN1744354 A CN 1744354A CN A200510096132X A CNA200510096132X A CN A200510096132XA CN 200510096132 A CN200510096132 A CN 200510096132A CN 1744354 A CN1744354 A CN 1744354A
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- 239000006182 cathode active material Substances 0.000 title claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004202 carbamide Substances 0.000 claims abstract description 43
- 239000000725 suspension Substances 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000011149 active material Substances 0.000 claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims description 46
- 230000004048 modification Effects 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 40
- 229910015645 LiMn Inorganic materials 0.000 claims description 26
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002019 doping agent Substances 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- 206010013786 Dry skin Diseases 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- 238000004804 winding Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229910013733 LiCo Inorganic materials 0.000 claims description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 5
- 229910012820 LiCoO Inorganic materials 0.000 claims description 3
- 229910013292 LiNiO Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910013184 LiBO Inorganic materials 0.000 claims description 2
- 229910014689 LiMnO Inorganic materials 0.000 claims description 2
- -1 ion salt Chemical class 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 3
- 239000012716 precipitator Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 2
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000005253 cladding Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910011687 LiCu Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013439 LiZr Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The method includes steps: first, preparing water solution of soluble doped ionic salt; next, mixing organic solvent with water solution; then, adding powder of active material for cathode to be modified to mixed solution, and mixing them to form suspension liquid; urea reflow is added to the suspension liquid; heating the suspension liquid to obtain modified powder of active material for cathode. Using hydrolysis of urea, the invention promotes generation of precipitator, making premonitory ion of modified oxide generate precipitation reaction. Adjusting condition of reaction, controlling speed of releasing precipitator, satisfying condition of heterogeneous nucleation makes all modified oxide develop on surface of active material for cathode so as to produce even and dense cladding precursor. Finally, doping ions in high concentration are formed on surface of active material. The invention improves cycle performance of cathode material markedly.
Description
Technical field
The present invention relates to the manufacture method of lithium-ion battery pole winding core needle, particularly a kind of surface modifying method of lithium-ion battery pole winding core needle.
Background technology
Owing to have advantages such as operating voltage height, energy density height, self discharge are little, environmental friendliness, memory-less effect, lithium ion battery has wide application in fields such as mobile phone, laptop computer, video camera, camera, portable entertainment audio-visual equipment, portable instrument and instrument, electric automobile, space flight power supplys, so lithium ion battery and correlation technique thereof become the focus and emphasis of whole world research and development.
At present, commercial lithium-ion battery pole winding core needle mainly adopts LiCoO
2, concentrate the active material of cathode of research that LiNiO is arranged
2, LiMn
2O
4, LiNi
xCo
(1-x)O
2, LiFePO
4Deng, but all there is a common problem in they: along with the repeated charge of battery, its discharge capacity descends gradually, i.e. circulation volume decay.
In order to suppress the capacity attenuation of active material of cathode, improve its cycle performance, the researcher has adopted the whole bag of tricks to improve its cycle performance, mainly comprises bulk phase-doped and surperficial coating:
(1) body is assorted disastrously mutually: people such as Hyung-Sun Kim adopt sol-gal process to synthesize LiM
xCo
1-xO
2[M=Mg, Zr] significantly improves LiCoO behind doped with Mg and the Zr
2Cycle performance, 50 all LiZr circulate
0.01Co
0.99O
2Specific capacity exceed LiCoO
230mAh/g[Journal of Power Sources 138 (2004) 232-239].At LiMn
2O
4The middle impurity zwitterion that adds forms LiMn
2-xM
xO
4-yN
y(M=Co, Ni, Cr, Fe, Al, Ti, B, V, Zn, Ge, Ga; N=F, Cl, S), these dopant ions can improve LiMn to a certain extent
2O
4Stability, suppress capacity attenuation.People such as M.Wakihara adopt Co
3O
4Li doped Mn
2O
4Form LiCo
1/6Mn
11/6O
4, studies show that: charge and discharge cycles is after 30 weeks, LiMn
2O
4Capacity attenuation reach 25%, and LiCo
1/6Mn
11/6O
4Only be 5% (Solid State Ionics 111 (1998) 153-159).People such as G.X.Wang and D.H.Bradhurst has studied and has mixed Cr front and back LiMn
2O
4Cycle performance, the result shows: LiMn
2O
4Though initial capacity reaches 130mAh/g, only be 90mAh/g after the circulation of 50 weeks, capacity attenuation 31.8%; LiCr
0.04Mn
1.96O
4Initial capacity is 122mAh/g, is 114mAh/g after the circulation of 50 weeks, capacity attenuation 6.6% (Solid State Ionics 120 (1999) 95-101).People such as F Croce adopt sol-gal process doping small amount of silver and copper, synthetic LiFePO
4Performance greatly improve, initial capacity has 140mAh/g, circulates to still have 130mAh/g[Electrochemical and solid stateletters, 2002,5 (3): A47-A50 after 30 times].
(2) surface coats: people such as Kannan utilize the stable Al of chemical property
2O
3Be coated on LiCoO
2The surface, initial specific capacity is near 180mAh/g, 100 all circulation volumes decay only have 8%, average each decay 0.08%[Electrochemical and Solid-State Letters, 2003,6 (1): A16-18].People such as WangZhaoxiang adopt direct precipitation method at LiCoO
2Oxide coated on surface MgO, the result shows LiCoO
2Structural stability be improved, effectively suppress the reaction of electrode surface and electrolyte, specific capacity reaches 210mAh/g[Journal of the electrochemical society, 2003,150 (2): A199-A208].At LiMn
2O
4The surface coats layer of substance, can effectively reduce LiMn
2O
4The dissolving of middle Mn improves its cycle performance.People such as D.Aurbach adopt MgO to coat LiMn
2O
4, discover: at 60 ℃ of circulate down 100 weeks, not LiMn of Bao Fuing
2O
4Capacity attenuation 22.1%; And the LiMn after coating
2O
4Decay to 12.3%, show excellent cycle performance (Electrochemistry Communications 5 (2003) 940-945).People such as Seung-Won Lee adopt sol-gel method at LiMn
2O
4The surface coats Al
2O
3, not only improved LiMn
2O
4Initial capacity, and improved LiMn
2O
4Cycle performance (Journal of PowerSources 126 (2004) 150-155).People such as Armand pass through at synthetic LiFePO
4The organic compound presoma of preceding carbon coated, initial specific capacity is 150mAh/g, and 1% capacitance loss [Journal of power sources, 2001,97-98:503-507] is only arranged in 10 weeks of circulating.
More than two kinds of methods pluses and minuses are respectively arranged, bulk phase-doped doping is big more, stability is good more, but the synthetic difficulty of material strengthens; Though it is less that the surface coats the energy doping, the improvement degree is limited.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide that a kind of preparation method is simple, processing ease, with short production cycle, production cost is low, and can significantly improve the surface modifying method of the lithium-ion battery pole winding core needle of its cycle performance.
For achieving the above object, the preparation method that the present invention adopts is: at first with the dopant ion salt M of solubility
xA
yBe mixed with the aqueous solution that concentration is 0.01-0.2mol/l, wherein M=Mg
2+, Zn
2+, Ni
2+, Cu
2+, Al
3+, Co
3+, Cr
3+, Fe
3+Or Ti
4+A=NO
- 3, Cl
-Or CH
3COO
-Then organic solvent is mixed by 2: 1～1: 10 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiBO that needs modification again by 10～300g/l
2Or LiN
ZMn
2-ZO
4, LiFePO
4Powder stir formation suspension, wherein B=Co
xNi
yMn
1-x-y, x=0-1, y=0-1, x+y≤1; N=Co, Ni, Ti, Cr or Cu, Z=0～0.5; In suspension, add urea by dopant ion and 1: 1～1: 10 mol ratio of urea, 70 ℃ of-100 ℃ of backflows, after continuing stirring and heating 2-20h, 60 ℃ of dry 20h in air, handle 5-20h at 200-600 ℃ of constant temperature subsequently, handle 1-20h at 600-1000 ℃ again, obtain the cathode active material powder of modification after the grinding.
Organic solvent of the present invention is methyl alcohol, ethanol, acetone or acetylacetone,2,4-pentanedione.
Because the present invention utilizes the hydrolysis of urea to facilitate the generation of precipitation reagent, makes the presoma ion generation precipitation reaction of modified oxide.By the adjusting of reaction condition, the rate of release of control precipitation reagent satisfies coating the condition of presoma at active material of cathode surface heterogeneous nucleation, allows modified oxide all in the growth of active material of cathode surface nucleation, produces the coating presoma of even compact.Make precipitation be decomposed into modified oxide more at a certain temperature, handle oxide coated active material of cathode at last at a certain temperature, form the dopant ion of high concentration on its surface, obtain the modification active material of cathode.
Description of drawings
Fig. 1 is LiMn
2O
4With employing modification LiMn of the present invention
2O
4Cycle performance figure under the 1C charge-discharge velocity, wherein abscissa is the circulation cycle, ordinate is a specific capacity;
Fig. 2 is modification LiMn of the present invention
2O
4Cycle performance figure under different charge-discharge magnifications, wherein abscissa is the circulation cycle, ordinate is a specific capacity.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment 1: at first with the Mg (NO of solubility
3)
2Be mixed with the aqueous solution that concentration is 0.2mol/l; Then methyl alcohol is mixed by 2: 1 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiMn that needs modification again by 10g/l
2O
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 1 mol ratio of urea, 70 ℃ of backflows, after continuing stirring and heating 20 hours, 60 ℃ of dryings are 20 hours in air, handled 5 hours at 600 ℃ of constant temperature subsequently, handled 10 hours at 800 ℃ again, obtain the cathode active material powder of modification after the grinding.
Referring to Fig. 1, LiMn
2O
4Initial capacity is 117.4mAh/g, cycle performance and less stable, and specific capacity only is 73.9mAh/g after the circulation of 190 weeks, specific capacity descends up to 37.1%; Modification LiMn
2O
4Specific capacity descend to some extent, be 107.1mAh/g to the maximum, cycle performance significantly improves, 190 week circulation back specific capacities are 104.5mAh/g, capacity attenuation only is that the specific capacity in 2.4%, the 190 week is apparently higher than LiMn
2O
4, as can be seen, adopt method of modifying of the present invention, significantly improved LiMn
2O
4Cycle performance and stability.
Referring to Fig. 2, under different multiplying powers, the LiMn of modification of the present invention
2O
4Specific capacity does not have to descend substantially, even under 20C high current charge-discharge condition, cycle performance and stable quite stable.Charge-discharge magnification is got back under the 1C after the 171st week, and specific capacity can return to the specific capacity of the same terms originally, visible modification LiMn
2O
4Show high rate during charging-discharging preferably.
Embodiment 2: at first with the ZnCl of solubility
2Be mixed with the aqueous solution that concentration is 0.08mol/l; Then ethanol is mixed by 1.5: 1 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiNiO that needs modification again by 300g/l
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 6 mol ratio of urea, 90 ℃ of backflows, after continuing stirring and heating 8 hours, 60 ℃ of dryings are 20 hours in air, handled 13 hours at 400 ℃ of constant temperature subsequently, handled 1 hour at 1000 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 3: at first with the Ni (CH of solubility
3COO)
2Be mixed with the aqueous solution that concentration is 0.1mol/l; Then acetone is mixed by 1: 5 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCoO that needs modification again by 80g/l
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 10 mol ratio of urea, 100 ℃ of backflows, after continuing stirring and heating 2 hours, 60 ℃ of dryings are 20 hours in air, handled 8 hours at 500 ℃ of constant temperature subsequently, handled 10 hours at 800 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 4: at first with the Cu (NO of solubility
3)
2Be mixed with the aqueous solution that concentration is 0.04mol/l; Then acetylacetone,2,4-pentanedione is mixed by 1: 10 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiMnO that needs modification again by 260g/l
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 3 mol ratio of urea, 80 ℃ of backflows, after continuing stirring and heating 15 hours, 60 ℃ of dryings are 20 hours in air, handled 20 hours at 200 ℃ of constant temperature subsequently, handled 14 hours at 700 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 5: at first with the AlCl of solubility
3Be mixed with the aqueous solution that concentration is 0.15mol/l; Then methyl alcohol is mixed by 1: 6 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCo that needs modification again by 150g/l
0.5Ni
0.5O
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 8 mol ratio of urea, 75 ℃ of backflows, after continuing stirring and heating 18 hours, 60 ℃ of dryings are 20 hours in air, handled 15 hours at 300 ℃ of constant temperature subsequently, handled 4 hours at 900 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 6: at first with the Co (CH of solubility
3COO)
3Be mixed with the aqueous solution that concentration is 0.01mol/l; Then ethanol is mixed by 1: 3 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCo that needs modification again by 50g/l
0.2Ni
0.2Mn
0.6O
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 2 mol ratio of urea, 85 ℃ of backflows, after continuing stirring and heating 10 hours, 60 ℃ of dryings are 20 hours in air, handled 18 hours at 270 ℃ of constant temperature subsequently, handled 6 hours at 850 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 7: at first with the Cr (NO of solubility
3)
3Be mixed with the aqueous solution that concentration is 0.06mol/l; Then acetone is mixed by 1: 8 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCo that needs modification again by 180g/l
0.5Mn
1.5O
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 5 mol ratio of urea, 95 ℃ of backflows, after continuing stirring and heating 5 hours, 60 ℃ of dryings are 20 hours in air, handled 12 hours at 360 ℃ of constant temperature subsequently, handled 12 hours at 750 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 8: at first with the FeCl of solubility
3Be mixed with the aqueous solution that concentration is 0.12mol/l; Then acetylacetone,2,4-pentanedione is mixed by 1: 2 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCr that needs modification again by 200g/l
0.2Mn
1.8O
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 7 mol ratio of urea, 78 ℃ of backflows, after continuing stirring and heating 16 hours, 60 ℃ of dryings are 20 hours in air, handled 10 hours at 480 ℃ of constant temperature subsequently, handled 2 hours at 950 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 9: at first with the Ti (CH of solubility
3COO)
4Be mixed with the aqueous solution that concentration is 0.18mol/l; Then ethanol is mixed by 1: 4 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCu that needs modification again by 120g/l
0.1Mn
1.9O
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 4 mol ratio of urea, 94 ℃ of backflows, after continuing stirring and heating 4 hours, 60 ℃ of dryings are 20 hours in air, handled 6 hours at 550 ℃ of constant temperature subsequently, handled 7 hours at 850 ℃ again, obtain the cathode active material powder of modification after the grinding.
Embodiment 10: at first with the ZnCl of solubility
2Be mixed with the aqueous solution that concentration is 0.06mol/l; Then ethanol is mixed by 1.2: 1 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiFePO that needs modification again by 80g/l
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 4 mol ratio of urea, 90 ℃ of backflows, after continuing stirring and heating 10 hours, 60 ℃ of dryings are 10 hours in air, handled 10 hours at 400 ℃ of constant temperature subsequently, handled 20 hours at 600 ℃ again, obtain the cathode active material powder of modification after the grinding.
Claims (10)
1, the surface modifying method of lithium-ion battery pole winding core needle is characterized in that:
1) at first with the dopant ion salt M of solubility
xA
yBe mixed with the aqueous solution that concentration is 0.01-0.2mol/l, wherein M=Mg
2+, Zn
2+, Ni
2+, Cu
2+, Al
3+, Co
3+, Cr
3+, Fe
3+Or Ti
4+A=NO
- 3, Cl
-Or CH
3COO
-
2) then organic solvent is mixed by 2: 1～1: 10 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiBO that needs modification again by 10～300g/l
2Or LiN
ZMn
2-ZO
4, LiFePO
4Powder stir formation suspension, wherein B=Co
xNi
yMn
1-x-y, x=0-1, y=0-1, x+y≤1; N=Co, Ni, Ti, Cr or Cu, Z=0～0.5;
3) in suspension, add urea by dopant ion and 1: 1～1: 10 mol ratio of urea, 70 ℃ of-100 ℃ of backflows, after continuing stirring and heating 2-20h, 60 ℃ of dry 20h in air, handle 5-20h at 200-600 ℃ of constant temperature subsequently, handle 1-20h at 600-1000 ℃ again, obtain the cathode active material powder of modification after the grinding.
2, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: said organic solvent is methyl alcohol, ethanol, acetone or acetylacetone,2,4-pentanedione.
3, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first with the Mg (NO of solubility
3)
2Be mixed with the aqueous solution that concentration is 0.2mol/l; Then methyl alcohol is mixed by 2: 1 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiMn that needs modification again by 10g/l
2O
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 1 mol ratio of urea, 70 ℃ of backflows, after continuing stirring and heating 20 hours, 60 ℃ of dryings are 20 hours in air, handled 5 hours at 600 ℃ of constant temperature subsequently, handled 10 hours at 800 ℃ again, obtain the cathode active material powder of modification after the grinding.
4, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first the ZnCl2 with solubility is mixed with the aqueous solution that concentration is 0.08mol/l; Then ethanol is mixed by 1.5: 1 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiNiO that needs modification again by 300g/l
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 6 mol ratio of urea, 90 ℃ of backflows, after continuing stirring and heating 8 hours, 60 ℃ of dryings are 20 hours in air, handled 13 hours at 400 ℃ of constant temperature subsequently, handled 1 hour at 1000 ℃ again, obtain the cathode active material powder of modification after the grinding.
5, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first with the Ni (CH of solubility
3COO)
2Be mixed with the aqueous solution that concentration is 0.1mol/l; Then acetone is mixed by 1: 5 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCoO that needs modification again by 80g/l
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 10 mol ratio of urea, 100 ℃ of backflows, after continuing stirring and heating 2 hours, 60 ℃ of dryings are 20 hours in air, handled 8 hours at 500 ℃ of constant temperature subsequently, handled 10 hours at 800 ℃ again, obtain the cathode active material powder of modification after the grinding.
6, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first with the Cu (NO of solubility
3)
2Be mixed with the aqueous solution that concentration is 0.04mol/l; Then acetylacetone,2,4-pentanedione is mixed by 1: 10 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiMnO that needs modification again by 260g/l
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 3 mol ratio of urea, 80 ℃ of backflows, after continuing stirring and heating 15 hours, 60 ℃ of dryings are 20 hours in air, handled 20 hours at 200 ℃ of constant temperature subsequently, handled 14 hours at 700 ℃ again, obtain the cathode active material powder of modification after the grinding.
7, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first with the AlCl of solubility
3Be mixed with the aqueous solution that concentration is 0.15mol/l; Then methyl alcohol is mixed by 1: 6 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCo that needs modification again by 150g/l
0.5Ni
0.5O
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 8 mol ratio of urea, 75 ℃ of backflows, after continuing stirring and heating 18 hours, 60 ℃ of dryings are 20 hours in air, handled 15 hours at 300 ℃ of constant temperature subsequently, handled 4 hours at 900 ℃ again, obtain the cathode active material powder of modification after the grinding.
8, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first with the Co (CH of solubility
3COO)
3Be mixed with the aqueous solution that concentration is 0.01mol/l; Then ethanol is mixed by 1: 3 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCo that needs modification again by 50g/l
0.2Ni
0.2Mn
0.6O
2The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 2 mol ratio of urea, 85 ℃ of backflows, after continuing stirring and heating 10 hours, 60 ℃ of dryings are 20 hours in air, handled 18 hours at 270 ℃ of constant temperature subsequently, handled 6 hours at 850 ℃ again, obtain the cathode active material powder of modification after the grinding.
9, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first with the Cr (NO of solubility
3)
3Be mixed with the aqueous solution that concentration is 0.06mol/l; Then acetone is mixed by 1: 8 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCo that needs modification again by 180g/l
0.5Mn
1.5O
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 5 mol ratio of urea, 95 ℃ of backflows, after continuing stirring and heating 5 hours, 60 ℃ of dryings are 20 hours in air, handled 12 hours at 360 ℃ of constant temperature subsequently, handled 12 hours at 750 ℃ again, obtain the cathode active material powder of modification after the grinding.
10, the surface modifying method of lithium-ion battery pole winding core needle according to claim 1 is characterized in that: at first with the FeCl of solubility
3Be mixed with the aqueous solution that concentration is 0.12mol/l; Then acetylacetone,2,4-pentanedione is mixed by 1: 2 volume ratio with the aqueous solution, in this mixed liquor, add the active material of cathode LiCr that needs modification again by 200g/l
0.2Mn
1.8O
4The powder formation suspension that stirs; In suspension, add urea by dopant ion and 1: 7 mol ratio of urea, 78 ℃ of backflows, after continuing stirring and heating 16 hours, 60 ℃ of dryings are 20 hours in air, handled 10 hours at 480 ℃ of constant temperature subsequently, handled 2 hours at 950 ℃ again, obtain the cathode active material powder of modification after the grinding.
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| CN101777647A (en) * | 2010-02-11 | 2010-07-14 | 东莞新能源科技有限公司 | Lithium ion battery surface clad anode material and preparation method thereof |
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| CN101950803A (en) * | 2010-05-17 | 2011-01-19 | 东莞新能源科技有限公司 | Preparation method of cathode material of lithium ion battery coated with metal oxides on surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5931182B2 (en) * | 1975-12-17 | 1984-07-31 | 日立マクセル株式会社 | Manufacturing method of non-aqueous electrolyte battery |
| KR100347882B1 (en) * | 2000-07-11 | 2002-08-10 | 학교법인 서강대학교 | Conducting Polymer/Manganese Oxide Composite Cathode Material for Lithium Secondary Batteries and Method for Making Same |
| JP4740409B2 (en) * | 2003-06-11 | 2011-08-03 | 株式会社日立製作所 | Lithium secondary battery for electric vehicle or hybrid vehicle |
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| CN103178258B (en) * | 2013-01-21 | 2017-12-26 | 宁德新能源科技有限公司 | Alumina-coated is modified the preparation method of lithium nickel cobalt manganese oxygen positive electrode |
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| CN105473508A (en) * | 2013-08-19 | 2016-04-06 | 陶氏环球技术有限责任公司 | Improved lithium metal oxide rich cathode materials and method to make them |
| CN105473508B (en) * | 2013-08-19 | 2018-10-12 | 陶氏环球技术有限责任公司 | The improved cathode material rich in lithium metal oxide and its manufacturing method |
| CN105762348A (en) * | 2016-05-18 | 2016-07-13 | 浙江瓦力新能源科技有限公司 | Preparation method of battery cathode material with surface coated with composite oxides |
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