CN101780983A - Spinel Li1+xMyMn2-x-yO4, preparation method thereof and lithium-ion secondary battery - Google Patents
Spinel Li1+xMyMn2-x-yO4, preparation method thereof and lithium-ion secondary battery Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 33
- 239000011029 spinel Substances 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 229910006884 Li1+xMyMn2-x-yO4 Inorganic materials 0.000 title abstract 3
- 229910006878 Li1+xMyMn2−x−yO4 Inorganic materials 0.000 title abstract 3
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 40
- 238000005245 sintering Methods 0.000 claims description 30
- 238000000137 annealing Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000011164 primary particle Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 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
- 238000001228 spectrum Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 229910052748 manganese Inorganic materials 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
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 56
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- 238000009831 deintercalation Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
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- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 abstract 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 abstract 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 37
- 239000007774 positive electrode material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000009766 low-temperature sintering Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
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- -1 poly(vinylidene fluoride) Polymers 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000011010 synthetic spinel Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 1
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Images
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a lithium manganese oxide material, i.e. a spinel Li1+xMyMn2-x-yO4, wherein x is less than 0.1 and more than 0, y is less than 0.1 and more than 0, and M is selected from one or a plurality of Mg, Na, Co and Al; the ratio of the 400 crystal face diffraction peak strength I400 to 311 crystal face diffraction peak strength I311 of the Li1+xMyMn2-x-yO4 is 1.05-1.25; the atomic arrangement in crystal of the material is more ordered; the crystallinity degree of the material is higher, and fewer oxygen defects in a crystal lattice exist, thereby being more favourable for the lithium ion intercalation and deintercalation process in the crystal lattice and effectively inhibiting the Jahn-Teller effect to obviously improve the cycle performance of the material; and meanwhile, the invention also provides a preparation method of the material and is simple and easy to realize process. The invention also provides a lithium-ion secondary battery using the material, and the lithium-ion secondary battery has higher specific capacity and cycle performance, especially the high-temperature cycle performance, and satisfies the requirements of the existing battery development.
Description
Technical field
The present invention relates to a kind of doped spinel lithium manganate, relate in particular to a kind of spinel Li
1+xM
yMn
2-x-yO
4And preparation method thereof and lithium-ion secondary cell
Background technology
The energy, environment, information technology are three big themes of 21st century development in science and technology.Be accompanied by the continuous deterioration of the exhaustion day by day of traditional energy and mass consumption, seek clean, reproducible secondary energy and be and realize that human social is badly in need of solving of task global environment.In numerous secondary cell systems, lithium ion battery have operating voltage height, energy density big, have extended cycle life, advantages such as self-discharge rate is little, environmental protection, become the secondary cell main development tendency.Be widely used in cableless communication, digital camera, the power supply of portable electricity consuming productses such as notebook computer, and be used as vehicle using motor, and electric bicycle, battery-operated motor cycle, mine lamp, power tool, hybrid vehicle, the electrodynamic source aspect of pure electric vehicle has broad application prospects.
As anode material for lithium-ion batteries, LiCoO
2, LiMn
2O
4, LiNiO
2Be considered to the most attractive positive electrode material.Laminate structure LiCoO is mainly adopted in commercialization at present
2, it has synthetic easy, the stable advantage of charge-discharge performance, but also comes with some shortcomings: LiCoO
2Need rare, the expensive cobalt metal of ample resources when synthetic, thereby the material cost of battery is higher; Charging state LiCoO
2Thermally-stabilised poor, make with LiCoO
2Not good enough for battery security under abuse conditions of positive electrode material, can not satisfy the needs of power cells such as electric vehicle power sources, thereby hinder the development of lithium cell.Same LiNiO
2Also have unstable under the high-voltage and the potential safety hazard under the abuse conditions, in addition also difficulty relatively of the preparation of this material.Existing research is spinel lithium manganate more widely, have that resource is extensive, cheap, charge and discharge platform is high, under the abuse conditions security good, to advantages such as environment are nontoxic, be the particularly the most attractive positive electrode material of power-type lithium ion battery of lithium ion battery of future generation.
But conventional spinel lithium manganate itself remains in some shortcomings, mainly is that its capacity attenuation in working cycle is tighter, and the existing reason of analyzing the lithium manganate capacity attenuation mainly contains:
1) ginger-Taylor effect causes the variation of material structure;
2) manganic disproportionation reaction causes the dissolving of a small amount of manganese in electrolytic solution;
3) capacity attenuation that causes of the defective of oxygen.
And the method for synthetic spinel lithium manganate mainly contains sol-gel method and high temperature solid phase synthesis at present.Wherein sol-gel method can realize the mixing of raw material on the atom level level, and required synthesis temperature is low, and pattern is regular, but exist synthesis technique complexity, cost height, products therefrom density low, be difficult to shortcomings such as industrialization.And high temperature solid-state method generally adopts electrolytic manganese dioxide is presoma, with Li source compounds such as Quilonum Retard, lithium hydroxide at 600 ℃ of-900 ℃ of lithium manganates through the high temperature solid state reaction synthetic spinel, this method is compared with sol-gel method, though there is the synthesis temperature height, long reaction time, the shortcoming that energy consumption is big, but simple owing to its operation, be easy to industrial applications and become industrial main method, yet adopt the synthetic lithium manganate of conventional art high temperature solid-state to remain in some shortcomings:
(1) the raw material mixing is even inadequately, causes the pattern irregularity of lithium manganate, and thing is mutually inhomogeneous.
(2) temperature of reaction height is easy to generate a spot of dephasign in the product, cause the reduction of material specific capacity.And the synthetic material often forms the anoxybiotic structure easily under the high temperature, thereby reduces the cycle performance of material.
Therefore traditional high temperature solid-state building-up reactions is improved, be aided with means such as doping vario-property, composite structure is stable, pattern is regular, the specific storage height, the lithium manganate that normal temperature and high temperature cyclic performance are good, for promoting that lithium ion battery further develops, promote the industrialization of electric vehicle lithium ion battery and have important significance for theories and practical value.
Summary of the invention
The present invention is in order to overcome the lithium manganate pattern irregularity of prior art for preparing, thing phase heterogeneity, and contain dephasign, cause material specific capacity low, form the anoxic structure simultaneously easily, reduce the shortcoming of material cycle performance, a kind of thing phase homogeneous is provided, pattern is regular, doped spinel lithium manganate of high conformity and preparation method thereof and contain the specific storage height of this material, the lithium-ion secondary cell of good cycle.
A kind of spinel Li
1+xM
yMn
2-x-yO
4, wherein, 0＜x＜0.1,0＜y＜0.1, M is selected from one or more among Mg, Na, Co, the A1, Li
1+xM
yMn
2-x-yO
4(400) crystal face diffraction peak intensity I
400With (311) crystal face diffraction peak intensity I
311Ratio be 1.05～1.25.
Above-mentioned spinel Li
1+xM
yMn
2-x-yO
4The preparation method, comprise
(1) batch mixing: with lithium-containing compound, manganese powder and/or contain manganic compound and contain doping element compound and mix by chemical dosage ratio, add solvent and stir evenly, change ball milling in the ball grinder over to, drying desolventizes, mixing raw material;
(2) step (1) gained mixing raw material is carried out sintering containing under the atmosphere of oxygen;
(3) with step (2) gained Li
1+xM
yMn
2-x-yO
4Presoma contains the sintering of annealing under the atmosphere of oxygen; Cooling obtains Li
1+xM
yMn
2-x-yO
4
A kind of lithium-ion secondary cell comprises positive plate, negative plate, barrier film, electrolytic solution, wherein, contains above-mentioned spinel Li in the positive plate
1+xM
yMn
2-x-yO
4
The unexpected doped spinel lithium manganate crystallization degree of finding that the present invention obtains of the present inventor obviously improves, and it is perfect more that crystal formation becomes, and the oxygen defect in the crystal is few, and the order degree of each atomic arrangement obviously improves.Can significantly find out the X-ray diffraction spectrum of more common lithium manganate from the X-ray diffraction spectrum of material and sem photograph, characteristic diffraction peak of the present invention is stronger, particularly (311) crystal face diffraction peak intensity I
311/ I
111For with (400) crystal face diffraction peak intensity I
400/ I
111All greater than 45%, and I
311And I
400Difference between 5%-10%, differ bigger, and the I of existing lithium manganate
311And I
400Difference generally below 2%, show that atomic arrangement is more orderly in the crystal of material, the crystallization degree of material is higher, the defective of oxygen still less in the lattice, this will help lithium ion more and take off embedding in lattice, and can effectively suppress ginger-Taylor effect, and the cycle performance of material obviously improves; And (111) crystal face diffraction peak intensity I with respect to existing lithium manganate
111Less than 2500, (311) crystal face diffraction peak intensity I
311/ I
111(400) crystal face diffraction peak intensity I
400/ I
111All less than 40%, (111) crystal face diffraction peak intensity I of the lithium manganate of synthetic materials of the present invention
111Greater than 3000, the intensity at peak is higher, shows that the pattern of material is more regular, and thing is more even mutually, high conformity; Scheme us from SEM and can find out obviously that also the spinel pattern of synthetic lithium manganate of the present invention is very obvious, crystal formation is more complete, and the lithium manganate of more existing general primary particle particle diameter below 500nm, lithium manganate primary particle of the present invention is bigger, general all between 1-3 μ m, thereby can reduce the contact area of material and electrolytic solution, reduce the dissolving of Mn in the charge and discharge process, improve the cycle performance of material.Preparation method of the present invention is simple simultaneously, more easily realizes technology.
The present invention has beneficial effect:
1) reaction raw materials of the present invention can mix on higher rank by means such as liquid-phase mixing and dynamic dryings, and it is mutually even to help synthetics, and pattern is regular, the doped spinel lithium manganate of high conformity.
2) by mixing, help the stable spinel lithium manganate of composite structure, suppressed the structural changes that ginger-Taylor effect causes to a certain extent.
3) by means such as multistage roasting and annealing, help the synthetic few spinel lithium manganate of oxygen defect, improved the cycle performance of material.
Battery specific storage with material preparation of the present invention can reach 112mAh/g, has higher specific storage; And the 1C circulation is 200 times under the normal temperature, and capability retention can reach 95%, 45 ℃ of following 1C circulation 200 times, and capability retention can reach 89%, and the high temperature cyclic performance of battery is good, satisfies the demand of existing battery development.
Description of drawings
Fig. 1 is the SEM figure of the lithium manganate of Comparative Examples 1 preparation;
Fig. 2 is the XRD figure of the lithium manganate of Comparative Examples 1 preparation;
Fig. 3 is the SEM figure of the lithium manganate of embodiment 1 preparation;
Fig. 4 is the XRD figure of the lithium manganate of embodiment 1 preparation;
Fig. 5 is the charging and discharging curve of the battery of embodiment 1 preparation;
Fig. 6 is 45 ℃ of cycle performance curves of the battery of embodiment 1 preparation.
Embodiment
The present invention is in order to overcome the lithium manganate pattern irregularity of prior art for preparing, thing phase heterogeneity, and contain dephasign, cause material specific capacity low, form the anoxic structure simultaneously easily, reduce the shortcoming of material cycle performance, a kind of thing phase homogeneous is provided, pattern is regular, doped spinel lithium manganate of high conformity and preparation method thereof and contain the specific storage height of this material, the lithium-ion secondary cell of good cycle.
A kind of spinel Li
1+xM
yMn
2-x-yO
4, wherein, 0＜x＜0.1,0＜y＜0.1, M is selected from one or more among Mg, Na, Co, the Al, Li
1+xM
yMn
2-x-yO
4(400) crystal face diffraction peak intensity I
400With (311) crystal face diffraction peak intensity I
311Ratio be 1.05～1.25, strength difference is bigger, atomic arrangement is more orderly in the crystal of material, the crystallization degree of material is higher, this will help lithium ion more and take off embedding in lattice, and can effectively suppress ginger-Taylor effect, and the cycle performance of material obviously improves.And the spinel structure and the grain morphology of the present invention's energy better controlled lithium manganate, the chemical property of lithium manganate is also improved significantly; The present invention simultaneously helps the stable spinel lithium manganate of composite structure by one or more elements among doped with Mg, Na, Co, the Al, has further suppressed the structural changes that ginger-Taylor effect causes.
Wherein, Li
1+xM
yMn
2-x-yO
4X-ray diffraction spectrum in, the peak width at half height B value at 111,311,400 peaks is all 0.18～0.200, the crystal formation of this illustrative material is more complete, crystal grain is bigger, helps reducing the dissolving of Mn in electrolytic solution, improves the cycle performance of the battery of preparation.
Wherein, Li
1+xM
yMn
2-x-yO
4(111) crystal face diffraction peak intensity I
111Greater than 3000, (311) crystal face diffraction peak intensity I
311/ I
111Value greater than 45%; (400) crystal face diffraction peak intensity I
400/ I
111Value greater than 50%, the intensity at peak is higher, the pattern of material is more regular, thing is mutually more even, high conformity.
Wherein, Li
1+xM
yMn
2-x-yO
4Satisfy the height≤1800 counting/seconds at 1000 counting/seconds≤311 peaks, the height at 2000 counting/seconds≤111 peaks≤3500 counting/seconds.
Simultaneously, Li of the present invention
1+xM
yMn
2-x-yO
4The primary particle diameter be preferably 1-3 μ m, this helps reducing the specific surface area of material, improves the cycle performance of battery.
The present invention provides above-mentioned spinel Li simultaneously
1+xM
yMn
2-x-yO
4The preparation method, comprise
(1) batch mixing: with lithium-containing compound, manganese powder and/or contain manganic compound and contain doping element compound and mix by chemical dosage ratio, add solvent and stir evenly, change ball milling in the ball grinder over to, drying desolventizes, mixing raw material;
(2) step (1) gained mixing raw material is carried out high temperature sintering containing under the atmosphere of oxygen;
(3) with step (2) gained Li
1+xM
yMn
2-x-yO
4Presoma contains the low-temperature sintering of annealing under the atmosphere of oxygen; Cooling obtains Li
1+xM
yMn
2-x-yO
4Preparation method of the present invention is simple, and cost is lower, is easy to realize.Being widely used of the spinel structure lithium manganate for preparing, and the performance of the product of application lithium manganate of the present invention all has significant improvement.
Wherein, the preferred lithium-containing compound of the present invention, manganese powder and/or the chemical dosage ratio that contains manganic compound and contain doping element compound are that the mol ratio of Li: Mn: M is 1.0～1.1: 1.6～2.0: 0.01～0.3, more preferably 1.05～1.1: 1.7～1.9: 0.05～0.3, this will more help suppressing ginger-Taylor effect, improve cycle performance.
Wherein, add solvent and stir evenly and can be the known various alr modes of ability, mechanical stirring etc. for example, the time of stirring is 0.5-6h.Wherein, ball milling the present invention be not particularly limited, and can select the equipment that well known to a person skilled in the art various high speed ball millings for use, for example roller ball mill or planetary ball mill, and ratio of grinding media to material is less than 3: 1, ball milling time 0.5-6h.
Wherein, the preferred drying of the present invention desolventizes to dynamic drying and desolventizes, drying is at 50-300 ℃, stirring and drying under the condition of negative pressure 0.05～0.1MPa, be 1-24h time of drying, is that the raw material mixing is more even by this method, and it is mutually even to help synthetics, pattern is regular, the doped spinel lithium manganate of high conformity.
Wherein, high temperature sintering the present invention be not particularly limited, can be various sintering well known in the art, can be once sintered also can be repeatedly sintering of segmentation, the preferred high temperature sintering of the present invention comprise mixing raw material 450-800 ℃ sintering 0.5-12 hour next time, then original position is warming up to 850-1000 ℃, carry out double sintering, sintering 0.5-24 hour, agglomerating equipment is not particularly limited, can select for use to well known to a person skilled in the art various stoves etc., adopt this multistage agglomerating technology can allow lithium salts and manganese salt initial reaction when low temperature on the one hand, can avoid a large amount of volatilizations of lithium salts under the high temperature on the other hand.Wherein, the said original position of the present invention heats up to well known to a person skilled in the art original position intensification implication, does not promptly take out the first sintering product from sintering oven, and the first sintering product directly is warming up to second sintering temperature without cooling.
Wherein, annealing low-temperature sintering the present invention be not particularly limited, and can be various annealing low-temperature sinterings well known in the art, can be that the low-temperature sintering of once annealing also can be the segmentation sintering of repeatedly annealing, and the present invention's low-temperature sintering of preferably annealing comprises Li
1+xM
yMn
2-x-yO
4The presoma sintering 1-24h that under 600 ℃-700 ℃, once anneals, then original position is cooled to 400-600 ℃ and carries out second annealing sintering 1-24h, and through second annealing, oxygen defect still less helps improving the cycle performance of material in the lattice of material.Wherein, the multistage annealing sintering can also can be warming up to the annealing temperature sintering with being quickly cooled to room temperature through the precursor after the high-temperature calcination again be cooled to the insulation of annealing sintering temperature through the precursor direct in-situ after the high-temperature calcination in the annealing furnace of special use.It is too high always that the present invention has overcome existing temperature of reaction, is easy to generate a spot of dephasign in the product, the material specific capacity of reduction, and low temperature insulation simultaneously helps the synthetic few spinel lithium manganate of oxygen defect, has improved the cycle performance of material.In order to suppress the high-temperature phase-change of product, annealing temperature can not be too high, can not be low excessively, and general annealed temperature is at 400-700 ℃; Simultaneously, the lithium phase transformation is lost in the long easy appearance of annealing time, and crossing does not lowly then have positive effect, so annealing time is 5-24 hour, and the over-all properties of the material of firing is better.
Wherein, high temperature sintering and the low sintering reaction atmosphere of annealing are the atmosphere that contains oxygen, can be for well known to a person skilled in the art various atmosphere, and for example air, pressurized air or oxygen atmosphere etc.
Wherein, solvent the present invention be not particularly limited, and preferred solvent of the present invention is a water, methyl alcohol, and ethanol, wherein, the mass ratio 0.3～1 of solvent load and solid matter.
Wherein, the preferred lithium-containing compound of the present invention is selected from one or more in lithium hydroxide, Quilonum Retard, lithium nitrate, the lithium acetate; Contain that manganic compound is selected from that manganous carbonate, manganous oxalate, manganous acetate, manganous nitrate, electrolytic manganese dioxide, chemical manganese bioxide, manganic oxide, four oxidations are three violent, in the manganese oxide one or more; Containing doping element compound is selected from and contains Mg, one or more in the carbonate of one or more elements among Na, Co, the Al, nitrate, acetate, the oxide compound.
Wherein, be cooled to the various common technology means that well known to a person skilled in the art.
The present invention provides a kind of lithium-ion secondary cell simultaneously, comprises positive plate, negative plate, barrier film, electrolytic solution, wherein, contains above-mentioned spinel Li in the positive plate
1+xM
yMn
2-x-yO
4
Because the present invention only relates to cathode plate for lithium secondary battery preparation method's improvement, therefore except described positive pole prepared according to method provided by the invention, other step was conventionally known to one of skill in the art.In general, comprise and will between positive pole and the negative pole barrier film be set, constitute the electrode group, this electrode group is contained in the battery container, inject electrolytic solution, the enclosed cell housing gets final product.
The present invention only relates to the improvement to the anode preparation method, and therefore the The Nomenclature Composition and Structure of Complexes to lithium secondary battery has no particular limits (unless outside the specified otherwise, the reagent that relates in the specific embodiment of the invention is commercially available analytical reagent).
Below in conjunction with embodiment the present invention is done more detailed description.
Embodiment 1
(1) preparation of positive electrode material
With 340g Quilonum Retard (cell-grade), 1400g electrolytic manganese dioxide, 70.22g Xiao Suangu (cobalt contents 21%), 95.32g ANN aluminium nitrate nonahydrate (cell-grade), the 825g deionized water joins in the stirred pot of 5L, after stirring 1.5h, be transferred in the ball grinder of 5L, the control ratio of grinding media to material is 1: 1, on planetary ball mill with the speed ball milling 2h of 150 commentaries on classics/min, material behind the ball milling is taking out behind (self-control, negative pressure 0.05Mpa) 150 ℃ of dry 4h on the rake formula Vacuumdrier.Dried material first speed with 5 ℃/min in retort furnace is warming up to 650 ℃, constant temperature 6h, then be warming up to 900 ℃ with the speed of 3 ℃/min again, constant temperature 12h, the speed with 5 ℃/min is cooled to 700 ℃ then, constant temperature 8h, speed with 5 ℃/min is cooled to 500 ℃ again, and constant temperature 6h directly takes out and is cooled to room temperature, grind 300 eye mesh screens, obtained spinel lithium manganate.
XRD performance test: use model that Japanese company of science (Rigaku) produces each embodiment and comparative example to be produced positive electrode material and carry out x-ray diffraction pattern (CuK α) and test by: D/MAX2200PC type XRD, experiment condition is: adopt the Cu target, voltage is 40kV, and electric current is 20mA.The x-ray diffraction pattern of Huo Deing (CuK α) by experiment
Can draw the I of material from scheming us
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1.
SEM performance test: adopt the JSM-5610LV scanning electronic microscope of JEOL company that synthetic sample is carried out displaing microstructure observing, and grain size and size are analyzed, get primary particle diameter such as table 1.
(2) preparation of positive plate
30 gram poly(vinylidene fluoride) (PVDF) are dissolved in 450 gram N-Methyl pyrrolidone (NMP) solvents make binder solution, 940 gram positive active materials that will mix in advance then and 30 gram acetylene black powder join in the above-mentioned solution, fully mix and make anode sizing agent; With tensile pulp machine this anode sizing agent is coated to thick 18 microns aluminium foil two sides equably, through 125 ℃ of vacuum and heating dryings 1 hour, be cut into the pole piece of millimeter (wide) * 140,485 millimeters (length) * 44 micron (thick), by the calendering of two-wheel roller press, the compacted density that makes positive electrode material is 3.3 gram/cubic centimetres.The positive active material that contains the 7.2-7.4 gram on every positive pole of gained.
(3) preparation of negative pole
950 gram graphite, 20 gram carbon fibers and 30 gram styrene-butadiene rubber(SBR) (SBR) are mixed.Adding 1500 milliliters water stirs and is made into cathode size, evenly be applied to 12 microns Copper Foil two sides with tensile pulp machine, through 125 ℃ of vacuum and heating dryings 1 hour, roll-in, cut-parts make the negative pole of 480 millimeters 45 millimeters (wide) * of (length) * 144 microns (thick), contain the graphite that 4.0-4.1 restrains on the every negative pole.
(4) preparation of electrolytic solution
With LiPF
6Be configured to LiPF with NSC 11801 (EC) and methylcarbonate (DMC)
6Concentration is the solution (volume ratio of EC/DMC is 1: 1) of 1 mol, obtains electrolytic solution.
(5) assembling of battery
The positive pole that above-mentioned (2) are obtained, the negative pole that (3) obtain are wound into the electrode group of a square lithium secondary battery with 25 microns polypropylene diaphragms, and this electrode group included in 5 millimeters * 34 millimeters * 50 millimeters the rectangular cell aluminum hull, pack in the battery case and weld, inject about 2.8 milliliters of the electrolytic solution that above-mentioned (4) obtain, square lithium secondary battery is made in sealing.
Join box hat and be assembled into 053450 side's case lithium ion secondary cell.
Synthetic method and battery production method are identical with embodiment 1, and difference is in the preparation of positive electrode material that it is 10.0g anhydrous sodium carbonate (analytical pure) that raw material contains doping element compound, 5.2g magnesium nitrate hexahydrate (analytical pure).
Record the I of material according to the method identical with embodiment 1
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1; Primary particle diameter such as table 1.
Synthetic method and battery production method are identical with embodiment 1, and difference is in the preparation of positive electrode material the material behind the ball milling at 150 ℃, stirring and drying under the condition of negative pressure 0.1MPa, and be 4h time of drying.
Record the I of material according to the method identical with embodiment 1
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1; Primary particle diameter such as table 1.
Synthetic method and battery production method are identical with embodiment 1, the drying that difference is the material behind the ball milling in the preparation of positive electrode material for static dry (120 ℃, 6h).
Record the I of material according to the method identical with embodiment 1
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1; Primary particle diameter such as table 1.
Embodiment 5
Synthetic method and battery production method are identical with embodiment 1, and difference is that annealing is sintered to 600 ℃ of sintering 16 hours in the preparation of positive electrode material.
Record the I of material according to the method identical with embodiment 1
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1; Primary particle diameter such as table 1.
Embodiment 6
Synthetic method and battery production method are identical with embodiment 1, and difference is that the speed that annealing in the preparation of positive electrode material is sintered to 5 ℃/min is cooled to 700 ℃, constant temperature 12h, and the speed with 5 ℃/min is cooled to 600 ℃, constant temperature 12h again.
Record the I of material according to the method identical with embodiment 1
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1; Primary particle diameter such as table 1.
Embodiment 7
Synthetic method and battery production method are identical with embodiment 1, and difference is that the speed that annealing in the preparation of positive electrode material is sintered to 5 ℃/min is cooled to 800 ℃, constant temperature 5h, and the speed with 5 ℃/min is cooled to 300 ℃, constant temperature 5h again.
Record the I of material according to the method identical with embodiment 1
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1; Primary particle diameter such as table 1.
Comparative Examples 1
Synthetic method and battery production method are identical with embodiment 1, and difference is directly to be cooled to room temperature with the speed of 5 ℃/min, not to the material low-temperature sintering of annealing.
Record the I of material according to the method identical with embodiment 1
400/ I
311Peak width at half height B value, the I of 111,311,400 peak crystal face diffraction peaks
311/ I
111, I
400/ I
111Data such as table 1; Primary particle diameter such as table 1.
Performance test
1, specific storage
Use BS-9300R secondary cell performance detection device respectively the battery of embodiment 1-7 and Comparative Examples 1 preparation to be carried out the loading capacity test.Test environment is 25 ℃, relative humidity 30%, and measuring method is as follows:
With the 0.2C current charges to 4.2V, 20 milliamperes of cut-off currents of charging, then with the 1C current discharge to 3.0V, the record discharge capacity value.And calculate the first discharge specific capacity of battery according to following formula.The result is as shown in table 1.
Positive active material weight * 100% of loading capacity/each positive plate of first discharge specific capacity=first
2, cycle performance test
(25 ℃) carry out constant current charge with the constant current of 600mA to the battery of embodiment 1-7 and Comparative Examples 1 preparation under the normal temperature condition, and charging rises to 4.2V at voltage and carries out constant voltage charge later on, by electric current 25mA by voltage 4.2V; Shelved 10 minutes, and to 3.0V, measured the initial discharge capacity that obtains battery with the current discharge of 600mA.After shelving 10 minutes, repeat above step, make the successive charge-discharge test, obtain the discharge battery capacity after battery circulates for 200 times, calculate the discharge capacitance of 200 circulation back batteries according to following formula.The result is as shown in table 1.
Discharge capacitance=200 time circulation back loading capacity/initial discharge capacity * 100%
Repeat above-mentioned circulation under 45 ℃ of conditions, circulate and write down capability retention, test result such as table 1 after 200 times.
Table 1
| Embodiment 1 | |
|
|
Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | |
| ??I 400/I 311 | ??1.15 | ??1.1 | ??1.07 | ??1.13 | ??1.1 | ??1.16 | ??1.06 | ??1.01 |
| ??B 111 | ??0.192 | ??0.197 | ??0.197 | ??0.199 | ??0.195 | ??0.190 | ??0.195 | ??0.225 |
| ??I 311/I 111(％) | ??49.3 | ??47 | ??48.1 | ??48.5 | ??49.3 | ??48 | ??48 | ??42.0 |
| ??I 400/I 111(％) | ??56.6 | ??51.7 | ??51.3 | ??54.8 | ??54.2 | ??55.7 | ??51 | ??42.6 |
| Primary particle diameter (μ m) | ??2.5 | ??2.0 | ??2.0 | ??1.8 | ??2.3 | ??2.8 | ??2.3 | ??0.2 |
| Embodiment 1 | |
|
|
Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | |
| Specific storage (mAh/g) | ??105 | ??112 | ??104.3 | ??104.6 | ??106 | ??108 | ??110 | ??100 |
| Under the normal temperature behind the cycle charge- |
??95 | ??93.4 | ??93 | ??92 | ??92.5 | ??94 | ??90 | ??87 |
| Behind 45 ℃ of following cycle charge- |
??89 | ??88 | ??87.5 | ??87.3 | ??87.5 | ??88 | ??85 | ??75 |
As can be seen from the above table, (400) crystal face diffraction peak intensity I of lithium manganate material of the present invention
400With (311) crystal face diffraction peak intensity I
311Ratio be I
400/ I
311Greater than 1.05, show that oxygen defect is few in the lattice of material, the arrangement of each atom is more orderly.In addition, peak width at half height B value is very little, shows that crystal grain is big more, shows that the material crystallization degree is high more.
And the specific storage with the battery of material preparation of the present invention is higher, can reach 112mAh/g, and has better cycle performance, the 1C circulation is 200 times under the normal temperature, capability retention can reach 95%, and particularly high temperature cyclic performance is more excellent, and 45 ℃ of following 1C circulate 200 times, capability retention can reach more than 85%, satisfies existing battery and develops the particularly demand of the power battery pack of high power discharge.
Claims (13)
1. spinel Li
1+xM
yMn
2-x-yO
4, wherein, 0＜x＜0.1,0＜y＜0.1, M is selected from one or more among Mg, Na, Co, the Al, it is characterized in that, described Li
1+xM
yMn
2-x-yO
4400 crystal face diffraction peak intensity I
400With 311 crystal face diffraction peak intensity I
311Ratio be 1.05～1.25.
2. spinel Li as claimed in claim 1
1+xM
yMn
2-x-yO
4, it is characterized in that described Li
1+xM
yMn
2-x-yO
4X-ray diffraction spectrum in, the peak width at half height B value at 111 peaks is 0.18～0.200.
3. spinel Li as claimed in claim 1
1+xM
yMn
2-x-yO
4, it is characterized in that described Li
1+xM
yMn
2-x-yO
4111 crystal face diffraction peak intensity I
111Greater than 3000,311 crystal face diffraction peak intensity I
311/ I
111Greater than 45%; 400 crystal face diffraction peak intensity I
400/ I
111Greater than 50%.
4. spinel Li as claimed in claim 3
1+xM
yMn
2-x-yO
4, it is characterized in that described Li
1+xM
yMn
2-x-yO
4Satisfy the height≤1800 counting/seconds at 1000 counting/seconds≤311 peaks, the height at 2000 counting/seconds≤111 peaks≤3500 counting/seconds.
5. spinel Li as claimed in claim 1
1+xM
yMn
2-x-yO
4, it is characterized in that described Li
1+xM
yMn
2-x-yO
4The primary particle diameter be 1-3 μ m.
6. spinel Li as claimed in claim 1
1+xM
yMn
2-x-yO
4The preparation method, wherein, 0＜x＜0.1,0＜y＜0.1, M is selected from one or more among Mg, Na, Co, the Al, it is characterized in that, this method comprises
(1) batch mixing: with lithium-containing compound, manganese powder and/or contain manganic compound and contain doping element compound and mix by chemical dosage ratio, add solvent and stir evenly, change ball milling in the ball grinder over to, drying desolventizes, mixing raw material;
(2) step (1) gained mixing raw material is carried out sintering containing under the atmosphere of oxygen;
(3) with step (2) gained Li
1+xM
yMn
2-x-yO
4Presoma is containing the sintering of annealing under the atmosphere of oxygen; Cooling obtains Li
1+xM
yMn
2-x-yO
4
7. preparation method according to claim 6 is characterized in that, described lithium-containing compound, manganese powder and/or the chemical dosage ratio that contains manganic compound and contain doping element compound are that the mol ratio of Li: Mn: M is 1～1.1: 1.6～2.0: 0.01～0.3.
8. preparation method according to claim 6 is characterized in that, described drying is at 50-300 ℃, stirring and drying under the condition of negative pressure 0.02～0.1MPa, and be 1-24h time of drying.
9. preparation method according to claim 6 is characterized in that, described sintering comprises mixing raw material at 450-800 ℃ of sintering 0.5～12 hour next time, and then original position is warming up to 850-1000 ℃, carries out double sintering, sintering 0.5～24 hour; Temperature rise rate is 5 ℃/min.
10. preparation method according to claim 6 is characterized in that, described annealing sintering comprises Li
1+xM
yMn
2-x-yO
4Presoma is once annealed under 600 ℃-700 ℃, insulation 1～24h, and then original position is cooled to 400-600 ℃ and carries out second annealing, insulation 1-24h; Rate of temperature fall is 3 ℃/min.
11. preparation method according to claim 6 is characterized in that, described solvent is one or more in water, methyl alcohol, the ethanol; The mass ratio 0.3～1 of described solvent load and solid matter.
12. preparation method according to claim 6 is characterized in that, described lithium-containing compound is selected from one or more in lithium hydroxide, Quilonum Retard, lithium nitrate, the lithium acetate; Describedly contain that manganic compound is selected from that manganous carbonate, manganous oxalate, manganous acetate, manganous nitrate, electrolytic manganese dioxide, chemical manganese bioxide, manganic oxide, four oxidations are three violent, in the manganese oxide one or more; The described doping element compound that contains is selected from and contains Mg, one or more in the carbonate of one or more elements among Na, Co, the Al, nitrate, acetate, the oxide compound.
13. a lithium-ion secondary cell comprises positive plate, negative plate, barrier film, electrolytic solution, it is characterized in that: contain spinel Li as claimed in claim 1 in the described positive plate
1+xM
yMn
2-x-yO
4
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