CN100547831C - Modified spinelle manganic acid lithium material, preparation method and lithium secondary battery - Google Patents
Modified spinelle manganic acid lithium material, preparation method and lithium secondary battery Download PDFInfo
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- CN100547831C CN100547831C CNB2006100205100A CN200610020510A CN100547831C CN 100547831 C CN100547831 C CN 100547831C CN B2006100205100 A CNB2006100205100 A CN B2006100205100A CN 200610020510 A CN200610020510 A CN 200610020510A CN 100547831 C CN100547831 C CN 100547831C
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- source compound
- ball milling
- manganic acid
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- 239000000463 material Substances 0.000 title claims abstract description 65
- TWFMKJHWXGLVDF-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O Chemical compound [Li].[Mn](=O)(=O)(O)O TWFMKJHWXGLVDF-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 7
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims abstract description 4
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims abstract description 4
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005303 weighing Methods 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 8
- 229910015645 LiMn Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229960004643 cupric oxide Drugs 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of modified spinelle manganic acid lithium material that is used for positive electrode material of lithium secondary cell, and described LiMn2O4 is the adulterated lithium manganate Li that is doped with other metallic elements X
aMn
2-bX
bO
4, wherein, X is at least a in chromium, gallium, aluminium, magnesium, titanium, copper, the zinc, 0.97≤a≤1.07,0＜b≤0.1; And, described adulterated lithium manganate Li
aMn
2-bX
bO
4The surface also have a coating layer, described coating layer comprises at least a in boron lithium composite xoide, cobalt lithium composite xoide, vanadium lithium composite xoide or the carbon-coating.The invention also discloses the preparation method of above-mentioned material and be the lithium secondary battery of positive electrode with this material.Modified spinelle manganic acid lithium material provided by the invention all has high magnification deep discharge performance preferably under normal temperature and hot environment, preparation methods simply is easy to control and operation simultaneously, and production cost is low, is easy to industrialization.
Description
Technical field
The present invention relates to electrochemical field, particularly relate to a kind of modified spinelle manganic acid lithium material that is used for positive electrode material of lithium secondary cell, this preparation methods and be the lithium secondary battery of positive electrode material with this material.
Background technology
Although LiCoO
2/ C series lithium ion battery is at mobile communication, laptop computer and shoot with video-corder on the portable electronics such as camera and be applied, but the deficient and expensive price limit of cobalt resource the popularization of this battery system aspect fixing electrical source of power such as peaking power source and electric motor car.Yet LiMn
2O
4/ C system then has the absolute predominance on the price, and characteristics such as its high security, high voltage, low pollution have more won the generally good of people in addition.But LiMn
2O
4Problem such as have the decay of serious irreversible capacity in material (55 ℃) circulation at high temperature or the storage process and capacity attenuation is very fast when the degree of depth discharges and recharges, this has become LiMn
2O
4Can/C system heavy industrialization, maximize and use, particularly key in application on the high current charge-discharge battery.
Influence LiMn
2O
4The reason of cycle performance mainly contain following some: the one, discharge and recharge and storage process in, electrolyte is at higher-pressure region and LiMn
2O
4Compatibility bad, easily at LiMn
2O
4Decompose on the surface; The 2nd, in cyclic process, LiMn
2O
4In Mn
3+Following disproportionation takes place:
Mn
3+→Mn
2++Mn
4+
The Mn that generates
2+Can be dissolved in the electrolyte, thereby cause the loss of active material and the destruction of crystal structure; The 3rd, the J-T distortion can take place under the situation of deep discharge, the part crystal structure is by cube changing the cubic phase that energy is lower, structure is more stable mutually into, lose original electro-chemical activity, and because the fracture and the efflorescence that do not match and can cause the positive electrode surface of lattice constant.
These people are proposed many ways solved it.Propose adulterated al, nickel or chromium as Chinese patent application CN200410044225.3 and suppress the J-T distortion, thereby, its cycle performance improved; Chinese patent application CN200410027362.6 proposes to coat one deck transition metal oxide film on the LiMn2O4 surface and suppresses Mn
3+Dissolving, thus its cycle performance improved.But experiment finds that cycle performance increased when these methods discharged and recharged in the normal temperature low range, but the serious phenomenon of capacity attenuation is suppressed well when the degree of depth discharges and recharges that particularly the degree of depth discharges and recharges under 55 ℃ of environment of high temperature.
Summary of the invention
One of the object of the invention is, at the deficiency of above technology, provides a kind of modified spinelle manganic acid lithium material, can be when containing the positive electrode of lithium secondary battery of nonaqueous electrolyte at it, and the performance when having deep discharge under better normal temperature and the high temperature.
Another object of the present invention is to, the preparation method of above-mentioned modified spinelle manganic acid lithium material is provided.
The present invention also aims to, a kind of non-aqueous lithium secondary battery that uses above-mentioned modified spinelle manganic acid lithium as positive electrode is provided.
For achieving the above object, the present invention takes following technical scheme:
The invention discloses a kind of modified spinelle manganic acid lithium material that is used for positive electrode material of lithium secondary cell, described LiMn2O4 is the adulterated lithium manganate Li that is doped with other metallic elements X
aMn
2-bX
bO
4, wherein, X is at least a in chromium, gallium, aluminium, magnesium, titanium, copper, the zinc, 0.97≤a≤1.07,0＜b≤0.1; And, described adulterated lithium manganate Li
aMn
2-bX
bO
4The surface also have a coating layer, described coating layer comprises at least a in boron lithium composite xoide, cobalt lithium composite xoide, vanadium lithium composite xoide or the carbon-coating.
The mol ratio of described coating layer and adulterated lithium manganate is greater than 0, is less than or equal to 0.01.
The invention also discloses the above-mentioned preparation method who is used for the modified spinelle manganic acid lithium material of positive electrode material of lithium secondary cell, described method comprises step:
(1) Li source compound is carried out ball milling;
(2) by stoichiometric proportion, the source compound of Li source compound behind the ball milling that step (1) is obtained and electrolytic manganese dioxide, X element carries out mix grinding;
(3) mixture that makes in 450～600 ℃ of temperature lower calcination steps (2) is afterwards again in 750～900 ℃ of sintering temperatures;
(4) product of step (3) that grinds, sieves makes the material primary product;
(5) oxide/hydroxide/salt with Li source compound and boron, cobalt or vanadium is dissolved in the polar organic solvent, perhaps the carbon source material with polarity is dissolved in the polar organic solvent, make coating solution, and the primary product that step (4) makes is carried out surface treatment with coating solution;
(6) product that step (5) is obtained is dried, is ground, sieves in 80～150 ℃, afterwards in 550～750 ℃ of sintering.
Described Li source compound comprises the hydroxide or the oxide of lithium salts, lithium, and described lithium salts comprises at least a in lithium carbonate, lithium nitrate, the lithium oxalate, and the source compound of described X element comprises hydroxide, oxide or the salt of X element.
Described step (1) ball milling is meant with the zirconia ball to be medium, and the ball milling time is 1～2 hour; Described step (2) mix grinding is meant with the zirconia ball to be medium, and the time is 2～6 hours.
In the described step (3), being 4～8 hours 450～600 ℃ of temperature lower calcination times, is 6～14 hours 750～900 ℃ of sintering temperature times; In the described step (6), being 8～20 hours at 80～150 ℃ of drying times, is 5～10 hours at 550～750 ℃ of sintering times.
In the described step (5), with coating solution primary product is carried out surface treatment and be meant, under continuous condition of stirring, primary product is added in the coating solution, and heating while stirring.
In the described step (5), described polar organic solvent is alcohol or ketone, a kind of in particular methanol, ethanol or the acetone, and in a specific embodiment of the present invention, the carbon source material of described polarity is preferably polyvinyl alcohol.
The invention also discloses with the lithium secondary battery of above-mentioned modified spinelle manganic acid lithium material as positive electrode.
Because adopted above scheme, the beneficial effect that the present invention is possessed is:
(1) spinelle manganic acid lithium material is carried out composite metal ion doped, improved the structural stability of material when degree of depth charge and discharge cycles effectively.Capability retention when (2) having improved further by the coating of the lithium manganese composite metal oxide after mixing being carried out surface metal composite oxides or carbon-coating that depth of material discharges and recharges, improved the compatibility of material and electrolyte, thereby, make its degree of depth charge/discharge capacity conservation rate under high temperature (55 ℃) environment be improved significantly.The capacity that normal temperature 3C, 5C, 7C charge and discharge keeps most of more than 90% of normal temperature 1C capacity that is; Circulate 200 times capability retention more than 85%, and considerable part surpasses 90%.Even the capacity that normal temperature 9C charges and discharge keeps also more than 70% of Da Changwen 1C capacity, 200 times the capability retention of circulating is more than 84%.Under 55 ℃ of conditions of high temperature, 1C and 7C charge and discharge the capacity overwhelming majority and reach normal temperature 1C and charge and discharge more than 85% of capacity, even surpass 96%; The capability retention major part of circulation after 100 times also reaches more than 85% under this condition.(3) preparation methods simply is easy to control and operation, and production cost is low, is easy to industrialization.
Description of drawings
Fig. 1 is the X diffraction pattern (XRD) of the anode active material of lithium ion secondary battery of embodiment 1 preparation;
Fig. 2 is each multiplying power discharging curve chart of the anode active material of lithium ion secondary battery of embodiment 1 preparation;
Fig. 3 is the charge-discharge performance figure of the anode active material of lithium ion secondary battery of embodiment 1 preparation;
Fig. 4 is each multiplying power discharging curve chart of Comparative Examples 1 positive electrode active materials;
Fig. 5 is the charge-discharge performance figure of Comparative Examples 1 positive electrode active materials;
Fig. 6 is each multiplying power discharging curve chart of Comparative Examples 2 positive electrode active materials;
Fig. 7 is the charge-discharge performance figure of Comparative Examples 2 positive electrode active materials.
Embodiment
Also the present invention is described in further detail in conjunction with the accompanying drawings below by specific embodiment.
Embodiment 1
Take by weighing LiOHH
2O 1Kg, and get in the zirconia ball adding ball grinding cylinder dry for standby behind the ball milling 2h by mass ratio 1.5: 1 (material weight/ball is heavy), 1: 1.96: 0.02 in molar ratio: 0.02 took by weighing LiOHH respectively
2O (ball milling), electrolytic manganese dioxide (EMD), titanium dioxide (TiO
2) and cupric oxide (CuO) put into ball grinding cylinder, and add behind the zirconia ball ball milling 4h heavy about 1 times in 500 ℃ of roasting 5h, then continue calcining 10h at 800 ℃, naturally cool to take out after the room temperature grind, sieve (about 300 orders) preliminary materials A 1.Li in molar ratio
2O-2B
2O
3/ preliminary material=0.5% takes by weighing LiOHH
2O and H
3BO
3Place beaker, and the dissolve with methanol that adds about 20 times of quality multiples makes LiOHH
2O-H
3BO
3The coating solution B 1 of/methyl alcohol.Add methyl alcohol amount generally according to economy principle and guarantee LiOHH
2O and H
3BO
3Abundant dispersion determine.Constantly (stirring speed about 300～500rpm) under the condition of stirring, prepared preliminary materials A 1 is added in the coating solution B 1, the about 4h of heating is placed in the baking oven in 150 ℃ of baking 12h while stirring, powder after the oven dry in 600 ℃ of roasting 6h, is naturally cooled to after the room temperature and grinds, gets final product after sieve (about 300 orders).
Prepare material shape in order to detect present embodiment, the material of getting the present embodiment preparation carries out the XRD test, and the result as shown in Figure 1.As shown in Figure 1: XRD material doped and the coating front and back compose the peak much at one, are spinel structure.Do not occur any new assorted peak in the spectrogram, show that the metal ion of doping is present in the material structure cell, the coating Li on surface
2O-2B
2O
3Exist with the amorphous glass attitude.For detecting the chemical property that present embodiment prepares material; get 91 parts of the materials of present embodiment preparation; 5 parts of conductive agents; 4 parts of binding agent Kynoar (PVDF) and an amount of N-methyl pyrrolidone (NMP) are made slurry; be coated in the two-sided positive plate that makes of aluminium foil, the attached charge level density of positive plate is 38mg/cm
2, be assembled into the battery that model is 423048A by ordinary production technology, on new prestige cell tester test its discharge and recharge and multiplying power cycle performance, high temperature charge-discharge performance.Its structure and electrochemical property test result are shown in accompanying drawing 2-3.As shown in Figure 2, material is when multiplying power discharging, and lithium ion takes off embedding duct very unobstructed (the mid portion collimation of each multiplying power discharging curve is fine), thereby material has good multiplying power and cycle performance.The capacity that charges and discharge as normal temperature 3C, 5C, 7C, 9C keeps being respectively 97.4%, 98.1%, 91.5% and 73.9% of normal temperature 1C capacity, and 200 times the capability retention of circulating is respectively 93.5%, 92.9%, 92.1% and 93.4%.55 ℃ of 1C of high temperature and the 7C capacity of charging and discharging are respectively normal temperature 1C and charge and discharge 97.8% and 96.2% of capacity, and the capability retention of circulation after 100 times is respectively 88.9% and 91.7% under this condition, and this material has high temperature deep discharge performance preferably.
Embodiment 2:
Take by weighing Li
2CO
31Kg, and get in the zirconia ball adding ball grinding cylinder dry for standby behind the ball milling 2h by mass ratio 1.5: 1 (material weight/ball is heavy), 0.5: 1.95: 0.015 in molar ratio: 0.02 took by weighing Li respectively
2CO
3(ball milling), electrolytic manganese dioxide (EMD), chromium oxide (Cr
2O
3) and aluminum nitrate (Al (NO
3)
3) put into ball grinding cylinder, and add behind the zirconia ball ball milling 4h heavy about 1 times in 450 ℃ of calcining 8h, then continue sintering 8h at 850 ℃, naturally cool to take out after the room temperature grind, sieve (about 300 orders) preliminary materials A 1.The preliminary material of C/=0.6% takes by weighing an amount of PVAC polyvinylalcohol and places beaker and add the dissolving of about 20 times ethanol and make PVA and coat solution B 1 in molar ratio, and institute adds the amount of ethanol and determines according to the abundant dispersion of economy principle and assurance PVA equally.Constantly (stirring speed about 300～500rpm) under the condition of stirring, prepared preliminary materials A 1 is added in the coating solution B 1, the about 4h of heating is placed in the baking oven in 120 ℃ of baking 16h while stirring, powder after the oven dry in 620 ℃ of roasting 6h, is naturally cooled to after the room temperature modified spinelle manganic acid lithium that grinds, can obtain being coated with carbon-coating after sieve (about 300 orders).
With this material is positive electrode active materials, being assembled into the electrochemical property test result that battery carries out by the mode of embodiment 1 is: the capacity that normal temperature 3C, 5C, 7C, 9C charge and discharge keeps being respectively 92.6%, 91.3%, 90.5% and 71.4% of normal temperature 1C capacity, and 200 times the capability retention of circulating is respectively 92.9%, 90.1%, 91.4% and 90.8%.55 ℃ of 1C of high temperature and the 7C capacity of charging and discharging are respectively normal temperature 1C and charge and discharge 96.9% and 92.2% of capacity, and the capability retention of circulation after 100 times is respectively 90.1% and 87.9% under this condition.
Take by weighing anhydrous LiNO
31Kg, and get in the zirconia ball adding ball grinding cylinder dry for standby behind the ball milling 2h by mass ratio 1.5: 1 (material weight/ball is heavy), 1.05: 1.94: 0.01 in molar ratio: 0.04 took by weighing LiNO respectively
3(ball milling), electrolytic manganese dioxide (EMD), gallium oxide (Ga
2O
3) and magnesium hydroxide (Mg (OH)
2) put into ball grinding cylinder, and add behind the zirconia ball ball milling 4h heavy about 1 times in 600 ℃ of roasting 4h, then continue calcining 14h at 800 ℃, naturally cool to take out after the room temperature grind, sieve (about 300 orders) preliminary materials A 1.Lithium carbonate in molar ratio: cobaltosic oxide: preliminary material=3: 2: 100 takes by weighing lithium carbonate, cobaltosic oxide places beaker, and the acetone solution that adds about 20 times of quality multiples makes lithium carbonate, cobaltosic oxide mixed solution B1, add acetone amount equally according to economy principle and guarantee that the abundant dispersion of lithium carbonate and cobaltosic oxide determines.Constantly (stirring speed about 300～500rpm) under the condition of stirring, prepared preliminary materials A 1 is added in the solution B 1, the about 4h of heating is placed in the baking oven in 100 ℃ of baking 18h while stirring, powder after the oven dry in 660 ℃ of roasting 7h, is naturally cooled to after the room temperature modified spinelle manganic acid lithium that can obtain being coated with the cobalt lithium composite xoide after grinding, sieving.
With this material is positive electrode active materials, being assembled into the electrochemical property test result that battery carries out by the mode of embodiment 1 is: the capacity that normal temperature 3C, 5C, 7C, 9C charge and discharge keeps being respectively 93.5%, 93.3%, 90.7% and 76.7% of normal temperature 1C capacity, and 200 times the capability retention of circulating is respectively 88.7%, 87.1%, 86.9% and 86.8%.55 ℃ of 1C of high temperature and the 7C capacity of charging and discharging are respectively normal temperature 1C and charge and discharge 98.6% and 87.1% of capacity, and the capability retention of circulation after 100 times is respectively 91.6% and 87.8% under this condition.
Embodiment 4
Take by weighing anhydrous LiNO
31Kg, and get in the zirconia ball adding ball grinding cylinder dry for standby behind the ball milling 2h by mass ratio 1.5: 1 (material weight/ball is heavy), take by weighing LiOHH
2O 1Kg, and get in the zirconia ball adding ball grinding cylinder dry for standby behind the ball milling 2h, 0.8: 0.24: 1.93 in molar ratio: respectively take by weighing LiOHH at 0.02: 0.02: 0.03 by mass ratio 1.5: 1 (material weight/ball is heavy)
2O (ball milling), LiNO
3(ball milling), electrolytic manganese dioxide (EMD), zinc oxide (ZnO), magnesium hydroxide (Mg (OH)
2) and cupric oxide (CuO) put into ball grinding cylinder, and add behind the zirconia ball ball milling 4h heavy about 1 times in 560 ℃ of roasting 7h, then continue calcining 11h at 840 ℃, naturally cool to take out after the room temperature grind, sieve preliminary materials A 1.Lithium carbonate in molar ratio: vanadic oxide: preliminary material=1: 1: 100 takes by weighing lithium carbonate, vanadic oxide places beaker, and adds about 20 times acetone solution and make lithium carbonate, vanadic oxide mixed solution B1.Constantly (stirring speed about 300～500rpm) under the condition of stirring, prepared preliminary materials A 1 is added in the solution B 1, the about 4h of heating is placed in the baking oven in 80 ℃ of baking 20h while stirring, powder after the oven dry in 600 ℃ of roasting 8h, is naturally cooled to after the room temperature modified spinelle manganic acid lithium that can obtain being coated with the vanadium lithium composite xoide after grinding, sieving.
With this material is positive electrode active materials, being assembled into the electrochemical property test result that battery carries out by the mode of embodiment 1 is: the capacity that normal temperature 3C, 5C, 7C, 9C charge and discharge keeps being respectively 90.8%, 90.3%, 88.9% and 71.6% of normal temperature 1C capacity, and 200 times the capability retention of circulating is respectively 90.7%, 89.6%, 85.2% and 84.3%.55 ℃ of 1C of high temperature and the 7C capacity of charging and discharging are respectively normal temperature 1C and charge and discharge 88.2% and 80.9% of capacity, and the capability retention of circulation after 100 times is respectively 87.6% and 81.5% under this condition.
Comparative Examples 1
The spinelle manganic acid lithium material that does not also coat with other metallic elements that do not mix is a positive electrode, is that negative material is made battery with graphite.Specific as follows: as to get 91 parts of the spinelle manganic acid lithium materials that above-mentioned other metallic elements that do not mix do not coat yet, 5 parts of conductive agents, 4 parts of binding agent PVDF and an amount of NMP make slurry, are coated in the two-sided positive plate that makes of aluminium foil, and the attached charge level density of positive plate is 40mg/cm
2, be assembled into the battery that model is 423048A by ordinary production technology, on new prestige cell tester test its discharge and recharge and multiplying power cycle performance, high temperature charge-discharge performance.As Fig. 4 is each the multiplying power discharging curve chart of the spinelle manganic acid lithium material that other metallic elements do not coat yet of not mixing, and Fig. 5 is the charge-discharge performance figure of the spinelle manganic acid lithium material that other metallic elements also do not coat of not mixing;
Comparative Examples 2
To be doped with other metallic elements but the spinelle manganic acid lithium material that coats not is a positive electrode, is that negative material is made battery with graphite.Specific as follows: get above-mentioned doping but 91 parts of the spinelle manganic acid lithium materials that do not coat, 5 parts of conductive agents, 4 parts of binding agent PVDF and an amount of NMP make slurry, are coated in the two-sided positive plate that makes of aluminium foil, and the attached charge level density of positive plate is 38mg/cm
2, be assembled into the battery that model is 423048A by ordinary production technology, on new prestige cell tester test its discharge and recharge and multiplying power cycle performance, high temperature charge-discharge performance.As Fig. 6 is to mix but each multiplying power discharging curve chart of the spinelle manganic acid lithium material that do not coat, and Fig. 7 mixes but the charge-discharge performance figure of the spinelle manganic acid lithium material that do not coat;
Find by contrast, other metallic elements of doping provided by the invention also carry out surface coated spinelle manganic acid lithium material all have high magnification deep discharge performance preferably under normal temperature and hot environments, preparation methods simply is easy to control and operation simultaneously, production cost is low, is easy to industrialization.
Claims (6)
1, the preparation method who is used for the modified spinelle manganic acid lithium material of positive electrode material of lithium secondary cell, described LiMn2O4 is the adulterated lithium manganate Li that is doped with other metallic elements X
aMn
2-bX
bO
4, wherein, X is at least a in chromium, gallium, aluminium, magnesium, titanium, copper, the zinc, 0.97≤a≤1.07,0＜b≤0.1; And, described adulterated lithium manganate Li
aMn
2-bX
bO
4The surface also have a coating layer, described coating layer comprises at least a in boron lithium composite xoide, cobalt lithium composite xoide, vanadium lithium composite xoide or the carbon, it is characterized in that: described method comprises step:
(1) Li source compound is carried out ball milling;
(2) by stoichiometric proportion, the source compound of Li source compound behind the ball milling that step (1) is obtained and electrolytic manganese dioxide, X element carries out mix grinding;
(3) mixture that makes in 450～600 ℃ of temperature lower calcination steps (2) is afterwards again in 750～900 ℃ of sintering temperatures;
(4) product of step (3) that grinds, sieves makes the material primary product;
(5) oxide, hydroxide or the salt with Li source compound and boron, cobalt or vanadium is dissolved in the polar organic solvent, perhaps the carbon source material with polarity is dissolved in the polar organic solvent, make coating solution, and the primary product that step (4) makes is carried out surface treatment with coating solution, describedly carry out surface treatment and be meant under continuous condition of stirring, primary product is added in the coating solution, and heating while stirring;
(6) product that step (5) is obtained is dried, is ground, sieves in 80～150 ℃, afterwards in 550～750 ℃ of sintering.
2, preparation method according to claim 1, it is characterized in that: described Li source compound comprises the hydroxide or the oxide of lithium salts, lithium, described lithium salts comprises at least a in lithium carbonate, lithium nitrate, the lithium oxalate, and the source compound of described X element comprises hydroxide, oxide or the salt of X element.
3, preparation method according to claim 1 and 2 is characterized in that: described step (1) ball milling is meant with the zirconia ball to be medium, and the ball milling time is 1～2 hour; Described step (2) mix grinding is meant with the zirconia ball to be medium, and the time is 2～6 hours.
4, preparation method according to claim 1 and 2 is characterized in that: in the described step (3), being 4～8 hours 450～600 ℃ of temperature lower calcination times, is 6～14 hours 750～900 ℃ of sintering temperature times; In the described step (6), being 8～20 hours at 80～150 ℃ of drying times, is 5～10 hours at 550～750 ℃ of sintering times.
5, preparation method according to claim 1 and 2 is characterized in that: in the described step (5), described polar organic solvent is alcohol or ketone, and the carbon source material of described polarity is a polyvinyl alcohol.
6, preparation method according to claim 5 is characterized in that: described alcohol or ketone are a kind of in methyl alcohol, ethanol or the acetone.
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| CNB2006100205100A CN100547831C (en) | 2006-03-14 | 2006-03-14 | Modified spinelle manganic acid lithium material, preparation method and lithium secondary battery |
| HK08103097.8A HK1109244A1 (en) | 2006-03-14 | 2008-03-18 | A kind of modified spinel li2mno4 material, its manufacture method and lithium secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100205100A CN100547831C (en) | 2006-03-14 | 2006-03-14 | Modified spinelle manganic acid lithium material, preparation method and lithium secondary battery |
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| CN100547831C true CN100547831C (en) | 2009-10-07 |
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| CN101702375B (en) * | 2009-11-16 | 2011-06-22 | 苏州大学 | Preparation method of element doping manganese dioxide electrode material for super capacitor |
| CN106935809A (en) * | 2010-01-07 | 2017-07-07 | 株式会社Lg化学 | Positive electrode active materials comprising lithium manganese oxide and the cathode mix comprising it |
| CN102195033B (en) * | 2010-03-09 | 2014-06-04 | 中国科学院过程工程研究所 | Method for preparing lithium battery anode material Li-Mn compound oxide at low temperature and lithium ion secondary battery |
| CN102195042A (en) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | High performance lithium ion battery anode material lithium manganate and preparation method thereof |
| CN102195035A (en) * | 2010-03-19 | 2011-09-21 | 江西省福斯特新能源有限公司 | Positive material for lithium ion battery and lithium ion battery with same |
| CN101841022A (en) * | 2010-05-13 | 2010-09-22 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing cathode material lithium manganate of lithium ion battery |
| CN102867949B (en) * | 2011-07-04 | 2015-09-30 | 微宏动力***（湖州）有限公司 | Lithium ion secondary battery anode material and preparation method thereof |
| CN102368545A (en) * | 2011-10-31 | 2012-03-07 | 四川大学 | Preparation technology of lithium manganate electrode material doping and surface fluoride cladding |
| US20140356714A1 (en) * | 2012-01-16 | 2014-12-04 | Robert Bosch Gmbh | Process for preparing a core-shell structured lithiated manganese oxide |
| CN102569770A (en) * | 2012-03-06 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Full-solid lithium secondary battery cathode material, preparation method thereof and full-solid lithium secondary battery |
| CN102637873B (en) * | 2012-03-27 | 2016-08-17 | 曾小毛 | A kind of lithium ion battery negative material and preparation method thereof |
| CN103066263B (en) * | 2013-01-14 | 2015-07-22 | 思伊纳化学科技（北京）有限公司 | Lithium ion battery positive material and preparation method thereof |
| CN104241629B (en) * | 2013-06-06 | 2016-03-23 | 中国科学院金属研究所 | A kind of modified spinelle manganic acid lithium material and preparation method thereof |
| CN103456941B (en) * | 2013-08-20 | 2015-07-22 | 中信大锰矿业有限责任公司大新锰矿分公司 | Power type lithium manganate and preparation method thereof |
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