CN104201342A - Method for improving physical property of lithium and manganese enriched lithium ion battery pole pieces - Google Patents
Method for improving physical property of lithium and manganese enriched lithium ion battery pole pieces Download PDFInfo
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- CN104201342A CN104201342A CN201410503805.8A CN201410503805A CN104201342A CN 104201342 A CN104201342 A CN 104201342A CN 201410503805 A CN201410503805 A CN 201410503805A CN 104201342 A CN104201342 A CN 104201342A
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- Prior art keywords
- lithium
- limn2o4
- material modified
- lithium manganese
- lifepo4
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000000704 physical effect Effects 0.000 title claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title abstract description 17
- 239000011572 manganese Substances 0.000 title abstract description 11
- 229910052748 manganese Inorganic materials 0.000 title abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 108
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 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
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 66
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 55
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000006258 conductive agent Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- 239000006230 acetylene black Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 239000005030 aluminium foil Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 2
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- YTXFOSVCYYHADT-UHFFFAOYSA-N 2,1,3-benzoxadiazol-5-ol Chemical compound C1=C(O)C=CC2=NON=C21 YTXFOSVCYYHADT-UHFFFAOYSA-N 0.000 abstract 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 4
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000004513 sizing Methods 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 29
- 210000004027 cell Anatomy 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 8
- 230000004087 circulation Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- -1 ethyl carbonate ester Chemical class 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000989 Alclad Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910015118 LiMO Inorganic materials 0.000 description 2
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 210000003771 C cell Anatomy 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229910016482 Ni0.4Co0.2Mn0.4 Inorganic materials 0.000 description 1
- HLVYJPIRLJGENQ-UHFFFAOYSA-N [Li].[O].[Mn].[Ni].[Li] Chemical compound [Li].[O].[Mn].[Ni].[Li] HLVYJPIRLJGENQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for improving the physical property of lithium and manganese enriched lithium ion battery pole pieces. The method comprises the following steps: during the manufacturing process of the lithium and manganese enriched lithium ion battery pole pieces, the surface of a pole fluid is firstly coated with a lithium and manganese enriched sizing agent and then coated with a sizing agent of a lithium iron phosphate modified material or lithium manganate or a sizing agent of a lithium manganate modified material after being dried, so that physical property improved lithium and manganese enriched lithium ion battery pole pieces are obtained after drying. Compared with the prior art, the surface of the lithium and manganese enriched material is coated with the lithium iron phosphate modified material, lithium manganate or the lithium manganate modified material, the phenomenon that irreversible electrochemical reaction occurs when the battery is charged to be 4.5 V above is restrained, the primary coulombic efficiency is improved and the cycling performance is improved; besides, the lithium iron phosphate modified material, lithium manganite or the lithium manganite modified material has a high coulombic efficiency, and after the surface of the lithium and manganese enriched material is coated with the lithium iron phosphate modified material, lithium manganite or the lithium manganite modified material, the overall coulombic efficiency of the materials can be improved , the preparation process is simple, and the industrial production is facilitated.
Description
Technical field
The present invention relates to technical field of lithium ion, especially about a kind of method of improving rich lithium manganese electrodes of lithium-ion batteries physical property.
Background technology
Lithium ion battery is due to advantages such as its energy density are high, and operating voltage is high, good cycle, and is widely used in mobile phone, notebook computer, the fields such as electric automobile.Along with lithium ion battery applications field expands, anode material for lithium-ion batteries is also had higher requirement, as higher energy density, cheap price, good cycle life, higher high rate performance etc.
Stratiform lithium-rich anode material xLi
2mnO
3(1-x) LiMO
2(M=Mn, Ni, Co, Ni
0.5mn
0.5, Cr, Ni
1/3co
1/3mn
1/3, Fe ...) be a kind of α-NaFeO
2type solid-solution material, by the Li of stratiform
2mnO
3and LiMO
2(M=Mn, Ni, Co, Ni
0.5mn
0.5, Cr, Ni
1/3co
1/3mn
1/3, Fe ...) form, with its distinctive height ratio capacity (200～300mAh/g), the outstanding performance such as circulation ability and new charge discharge mechanism, become the study hotspot of current lithium ion secondary battery anode material.
Chinese patent 102013481A, a kind of synthetic method of spherical gradient lithium-rich anode material, publication date: on April 13rd, 2011, disclose a kind of spherical gradient lithium-rich anode material xLi
2mnO
3(1-x) Li[Ni
0.4co
0.2mn
0.4] O
2the synthetic method of (0.1≤x≤0.4), with the spherical presoma [Ni of existing commercialization
0.4co
0.2mn
0.4] (OH)
2carry out Mn element coated, then, with the processing of the lithium hydroxide heat of mixing, 0.2C multiplying power electric current discharges and recharges, and the specific capacitance that discharges is first 242mAh/g, and after 50 circulations, specific capacity is 221mAh/g.Chinese patent 101694876A, on April 14 2010 publication date, lithium-rich manganese-based anode material and preparation method thereof, discloses rich lithium base anode material Li[Li
(1-2x)/3ni
x-am
ymn
(2-x)/3-b] O
2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof, adopts the synthetic presoma [Ni of reactor coprecipitation
(x-a)/[x+ (2-x)/3]m
y/[x+ (2-x)/3]mn
[(2-x)/3-b]/[x+ (2-x)/3]] (OH)
2, then, with lithium compound mixing high temperature sintering, 0.1C multiplying power electric current discharges and recharges, and putting first specific capacitance is 250mAh/g, and under the condition that discharges and recharges of 2.75-4.2V, 1C, putting first specific capacitance is 144mAh/g, and after 300 circulations, capability retention is 97%.
These materials have excellent chemical property, and still, the maximum problem that this class positive electrode exists is exactly in the time that initial charge is above to 4.5V, and irreversible electrochemical reaction: xLi occurs
2mnO
3(1-x) MO
2→ xMnO
2(1-x) MO
2+ xLi
2(when charging is less than 4.5V, there is reversible de-lithium reaction: xLi in O
2mnO
3(1-x) LiMO
2→ xLi
2mnO
3(1-x) MO
2+ (1-x) Li.), i.e. Li in material
+with Li
2the form of O is deviate from from structure cell, and when electric discharge, this part lithium ion cannot all be embedded into original structure cell again, causes material to have larger irreversible capacity first, and coulomb efficiency is lower, and cyclical stability is poor.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned existence, a kind of method of improving rich lithium manganese electrodes of lithium-ion batteries physical property is provided, in rich lithium manganese electrodes of lithium-ion batteries manufacturing process, first utmost point flow surface is coated with rich lithium manganese slurry, after dry, be coated with the material modified slurry of LiFePO4 or LiMn2O4 or the material modified slurry of LiMn2O4 thereon, the rich lithium manganese electrodes of lithium-ion batteries of the physical property that improves after being dried.
For achieving the above object, the invention provides a kind of method of improving rich lithium manganese electrodes of lithium-ion batteries physical property, comprise the following steps:
(1), take rich lithium manganese material, conductive agent, binding agent, make solvent with 1-Methyl-2-Pyrrolidone, collector is aluminium foil, slurry modulation evenly, through coating, dryly obtain rich lithium manganese electrodes of lithium-ion batteries;
(2), on the rich lithium manganese electrodes of lithium-ion batteries of preparation, be coated with the material modified slurry of LiFePO4 or LiMn2O4 or the material modified slurry of LiMn2O4, dry, roll-in, cut-parts make the rich lithium manganese electrodes of lithium-ion batteries that improves physical property.
Further, in step (1), the mass ratio of rich lithium manganese material, conductive agent, binding agent is 85～96:1～7:3～8; Described conductive agent is acetylene black, Ks-6; Described binding agent is Kynoar.
Further, described rich lithium manganese material is xLi
2mnO
3(1-x) LiMO
2, wherein M is Ni
0.5-y/2mn
0.5-y/2al
y, 0.002≤y≤0.15,0.05≤x≤0.95, particle diameter D50 is 5-15um, tap density is 1.5-2.1g/cm
3.
Further, the preparation method of the material modified slurry of the material modified slurry of LiFePO4 or LiMn2O4 or LiMn2O4 is in step (2), take the material modified or LiMn2O4 of LiFePO4 or LiMn2O4 is material modified, conductive agent, binding agent according to 88～94:3～5:3～7 ratio, slurry modulation evenly, to obtain final product; Described conductive agent acetylene black, Ks-6; Described binding agent is Kynoar.
Further, described LiFePO4 is material modified comprises LiFePO4 coated with carbon or/and adulterate, and particle diameter D50 is 0.9-6um, and tap density is 0.9-1.7g/cm
3.
LiFePO4 is material modified comprises that the LiFePO 4 material of coated with carbon, the doping of coated with carbon comprise metal or nonmetal doping, for example: Al, Mg, Zn, Zr,, Ni, Co, Fe, V, F, Cl etc.
Described LiMn2O4 or LiMn2O4 are material modified, and wherein LiMn2O4 is material modified comprises LiMn2O4 doping or/and surface is coated, and particle diameter D50 is 5-17um, and tap density is 1.5-2.5g/cm
3.
LiMn2O4 is material modified comprise doping (metal or nonmetal doping, for example: Al, Mg, Zn, Zr,, Ni, Co, Fe, V, F, Cl etc.) LiMn2O4, the LiMn2O4 on surface coated (clad material comprises metal oxide, nonmetal oxide, carbon, salt etc.), the LiMn2O4 of surface coated doping.
The described rich lithium manganese electrodes of lithium-ion batteries that improves physical property, wherein material modified the or LiMn2O4 of LiFePO4 or lithium manganate material account for the material modified or LiMn2O4 of LiFePO4 on pole piece or LiMn2O4 is material modified and rich lithium manganese material gross mass 0.5%～10%.
A kind of method of improving lithium-nickel-manganese-oxygen-lithium ion battery pole piece physical property of the present invention is coated with the material modified or LiMn2O4 of LiFePO4 or LiMn2O4 material modified on rich lithium manganese pole piece.Compare with prior art, the present invention has the following advantages: (1) at rich lithium manganese material surface-coated LiFePO4 material modified or LiMn2O4 or LiMn2O4 material modified, than simple in rich lithium manganese surface clad material technique, the uniformity is high; (2) or LiMn2O4 material modified at rich lithium manganese material surface-coated LiFePO4 or LiMn2O4 are material modified, have suppressed initial charge when above to 4.5V, and irreversible electrochemical reaction: xLi occurs
2mnO
3(1-x) MO
2→ xMnO
2(1-x) MO
2+ xLi
2o, has improved coulomb efficiency first, thereby improves cycle performance.In addition, the material modified or LiMn2O4 of LiFePO4 or LiMn2O4 be material modified, and to have coulomb efficiency high, can improve the entirety coulomb efficiency of material at rich lithium manganese material surface-coated; (3) the fail safe LFP>LMO>NMC>NC A>LCO of positive electrode, the structure similar of rich lithium manganese material and ternary NMC, fail safe is close, at rich lithium manganese material surface-coated LiFePO4, material modified or LiMn2O4 or LiMn2O4 are material modified, are conducive to fail safe and improve; (4) the material modified or LiMn2O4 of LiFePO4 or LiMn2O4 are material modified has a higher electric conductivity, improves the conductivity of pole piece, thereby improves high rate performance, cyclical stability; (5) the material modified or LiMn2O4 of LiFePO4 or LiMn2O4 material modified, rich lithium manganese material particle diameter and tap density are close, have close compacted density, the compatibility when being easy to the processing of material and discharging and recharging removal lithium embedded; (6) or LiMn2O4 material modified at rich lithium manganese material surface-coated LiFePO4 or LiMn2O4 are material modified, (rich lithium manganese material surface activity is high can to avoid rich lithium manganese material, under high voltage easily with electrolyte generation side reaction) directly contact minimizing side reaction with electrolyte; (7) preparation technology is simple, is easy to suitability for industrialized production; (8) rich lithium manganese material is xLi
2mnO
3(1-x) LiMO
2, wherein M is Ni
0.5-y/2mn
0.5-y/2al
y, 0.002≤y≤0.15,0.05≤x≤0.95, is to contain Al
3+ion, structural stability is high, in charge and discharge process, good cycling stability.
Brief description of the drawings
Fig. 1 is the prepared rich lithium manganese electrodes of lithium-ion batteries first charge-discharge cycle performance curve of comparative example 1 of the present invention;
Fig. 2 is the prepared pole piece discharge cycles performance curve of this comparative example 1, embodiment 1;
Fig. 3 is the prepared rich lithium manganese electrodes of lithium-ion batteries first charge-discharge cycle performance curve that improves physical property of the embodiment of the present invention 1;
Fig. 4 is this comparative example 2, embodiment 3 made battery capacity conservation rate-cycle-index performance curves.
Embodiment
Understand better technical scheme of the present invention for ease of those skilled in the art, below in conjunction with specific embodiment, the present invention is further elaborated.
Comparative example 1
A kind of rich lithium manganese method for preparing lithium ion battery pole pieces, its rich lithium manganese material is 0.5Li
2mnO
30.5LiNi
0.45mn
0.45al
0.1o
2, particle diameter D50 is 8.5um, tap density is 1.9g/cm
3, preparation method comprises the following steps.
Take rich lithium manganese material, conductive agent acetylene black, binding agent Kynoar PVDF according to 90:5:5 ratio, make solvent with 1-Methyl-2-Pyrrolidone, collector is aluminium foil, slurry modulation evenly, through coating, dryly obtain rich lithium manganese electrodes of lithium-ion batteries.
Be washed into circular pole piece, 85 DEG C of vacuumize 12 hours, carries out compressing tablet, and 85 DEG C of vacuumize 12 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1.5mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
As shown in Figure 1, this button cell is carried out to charge and discharge cycles test: charging/discharging voltage scope is 4.8～2.0V, be at charging and discharging currents under the condition of 0.1C (1C=220mA/g), charge and discharge specific capacity is first respectively 327.985mAh/g, 218.582mAh/g, and coulombic efficiency is 66.64% first.
As shown in Figure 2, charging/discharging voltage scope is 4.8～2.0V, circulate in for the 1-5 time under the condition that charging and discharging currents is 0.1C (1C=220mA/g), circulate in for the 6-55 time under the condition that charging and discharging currents is 0.2C, be at charging and discharging currents under the condition of 0.2C, first discharge specific capacity is 192.292mAh/g, and 50 specific capacities that circulate are 166.865mAh/g, capability retention is 86.78%, and cyclical stability is poor.
This button cell is carried out to high rate performance test: charging/discharging voltage scope is 4.8～2.0V, charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each multiplying power circulation 5 times.Wherein, 1C=220mA/g.High rate performance test result shows, 5C specific discharge capacity is about 65mAh/g, and high rate performance is poor.
Embodiment 1
A method of improving rich lithium manganese electrodes of lithium-ion batteries physical property, comprises the following steps.
Take rich lithium manganese material, conductive agent acetylene black, binding agent Kynoar PVDF according to 90:5:5 ratio, make solvent with 1-Methyl-2-Pyrrolidone (NMP), collector is aluminium foil, slurry modulation evenly, obtain rich lithium manganese electrodes of lithium-ion batteries through being coated with, being dried, its rich lithium manganese material is 0.5Li
2mnO
30.5LiNi
0.45mn
0.45al
0.1o
2, particle diameter D50 is 8.5um, tap density is 1.9g/cm
3.
According to 92:1.5:1.5:5 ratio take that LiMn2O4 is material modified, conductive agent acetylene black, conductive agent Ks-6, binding agent Kynoar PVDF, slurry modulation evenly, on above-mentioned rich lithium manganese electrodes of lithium-ion batteries, be coated with, dry, make the rich lithium manganese electrodes of lithium-ion batteries that improves physical property.Wherein, LiMn2O4 is material modified is LiNi
0.5mn
1.5o
4, particle diameter D50 is 12.5um, tap density is 2.2g/cm
3, material modified 5.5% of rich lithium manganese and the material modified quality summation of LiMn2O4 that account for of LiMn2O4.
Assembled battery method of testing is all with comparative example 1.
As shown in Figure 3, this button cell is carried out to charge and discharge cycles test: charging/discharging voltage scope is 4.8～2.0V, be at charging and discharging currents under the condition of 0.1C (1C=220mA/g), charge and discharge specific capacity is first respectively 295.432mAh/g, 235.813mAh/g, coulombic efficiency is 79.82% first, obviously improves coulomb efficiency first.
As shown in Figure 2, charging/discharging voltage scope is 4.8～2.0V, circulate in for the 1-5 time under the condition that charging and discharging currents is 0.1C (1C=220mA/g), circulate in for the 6-55 time under the condition that charging and discharging currents is 0.2C, be at charging and discharging currents under the condition of 0.2C, first discharge specific capacity is 227.716mAh/g, and 50 specific capacities that circulate are 224.566mAh/g, capability retention is 98.62%, and cyclical stability is better.
This button cell is carried out to high rate performance test: charging/discharging voltage scope is 4.8～2.0V, charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each multiplying power circulation 5 times.Wherein, 1C=220mA/g.High rate performance test result shows, 5C specific discharge capacity is still more than 105mAh/g, and high rate performance is better.
Embodiment 2
A method of improving rich lithium manganese electrodes of lithium-ion batteries physical property, comprises the following steps.
Take rich lithium manganese material, conductive agent acetylene black, binding agent Kynoar PVDF according to 90:5:5 ratio, make solvent with 1-Methyl-2-Pyrrolidone (NMP), collector is aluminium foil, slurry modulation evenly, obtain rich lithium manganese electrodes of lithium-ion batteries through being coated with, being dried, its rich lithium manganese material is 0.5Li
2mnO
30.5LiNi
0.45mn
0.45al
0.1o
2, particle diameter D50 is 8.5um, tap density is 1.9g/cm
3.
According to 91:2:2:5 ratio take that LiFePO4 is material modified, conductive agent (acetylene black), conductive agent (Ks-6) binding agent (Kynoar PVDF), slurry modulation evenly, on above-mentioned rich lithium manganese electrodes of lithium-ion batteries, be coated with, dry, make the rich lithium manganese electrodes of lithium-ion batteries that improves physical property.Wherein, LiFePO4 is material modified is carbon-coated LiFePO 4 for lithium ion batteries material, and carbon content is 2.1%, and particle diameter D50 is 2.5um, and tap density is 1.2g/cm
3, material modified 1% of rich lithium manganese and the material modified quality summation of LiFePO4 that account for of LiFePO4.
Assembled battery method of testing is all with comparative example 1.
This button cell is carried out to charge and discharge cycles test: charging/discharging voltage scope is 4.8～2.0V, be at charging and discharging currents under the condition of 0.1C (1C=220mA/g), first charge-discharge specific capacity is respectively 273.222mAh/g, 221.856mAh/g, and coulombic efficiency is 81.2% first.
Charging/discharging voltage scope is 4.8～2.0V, circulate in for the 1-5 time under the condition that charging and discharging currents is 0.1C (1C=220mA/g), circulate in for the 6-55 time under the condition that charging and discharging currents is 0.2C, be at charging and discharging currents under the condition of 0.2C, first discharge specific capacity is 212.642mAh/g, 50 specific capacities that circulate are 207.539mAh/g, and capability retention is 97.6%, and cyclical stability is better.
This button cell is carried out to high rate performance test: charging/discharging voltage scope is 4.8～2.0V, charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each multiplying power circulation 5 times.Wherein, 1C=220mA/g.High rate performance test result shows, 5C specific discharge capacity is still more than 100mAh/g, and high rate performance is better.
Comparative example 2
This comparative example provides a kind of rich lithium manganese lithium ion battery 0.3Li
2mnO
30.7LiNi
0.49mn
0.49al
0.02o
2/ C cell making process, its rich lithium manganese material is 0.3Li
2mnO
30.7LiNi
0.49mn
0.49al
0.02o
2, particle diameter D50 is 6.4um, tap density is 1.65g/cm
3, comprise the following steps.
1. anode pole piece is made: take rich lithium manganese material, conductive agent acetylene black, binding agent Kynoar PVDF according to 91:4:6 ratio, make solvent with 1-Methyl-2-Pyrrolidone (NMP), collector is aluminium foil, slurry modulation evenly, obtains rich lithium manganese electrodes of lithium-ion batteries through being coated with, being dried.
2. cathode pole piece is made: according to negative material graphite: acetylene black: LA132=93.5:1.5:5 ratio composite material, and do stirring solvent with distilled water and be modulated into slurry, make anode plate for lithium ionic cell through coating, dry, roll-in, cut-parts.
3. adopt above-mentioned positive and negative electrode pole piece, celgard2400 membrane coil to be coiled into battery, design capacity is 1Ah, and alclad plastic film carries out closedtop, side seal.Electrolyte is 1.5mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, in the glove box that is full of argon gas atmosphere, carry out battery liquid-filling.
4. battery carries out preliminary filling, changes into.
5. the electric pool gas after changing into is extracted out, heat-sealing, obtains product.
See Fig. 4, this battery is carried out to charge and discharge cycles test: charging/discharging voltage scope is 4.8～2.0V, charging and discharging currents is 0.5A, circulates 100 times, and capability retention is 88.76%, and cycle performance is poor.Cell thickness has increased by 15.8% than the front thickness of circulation, and the obvious inflatable of battery is serious, and security performance is poor.
Embodiment 3
The present embodiment provides a kind of method of improving rich lithium manganese electrodes of lithium-ion batteries physical property, and its rich lithium manganese material is 0.3Li
2mnO
30.7LiNi
0.49mn
0.49al
0.02o
2, particle diameter D50 is 6.4um, tap density is 1.65g/cm
3, the material that improves rich lithium manganese electrodes of lithium-ion batteries physical property is LiMn2O4, and particle diameter D50 is 8.5um, and tap density is 1.86g/cm
3, it comprises the following steps.
1. anode pole piece is made: take rich lithium manganese material, conductive agent acetylene black, binding agent Kynoar PVDF according to 91:4:6 ratio, make solvent with 1-Methyl-2-Pyrrolidone (NMP), collector is aluminium foil, slurry modulation evenly, obtains rich lithium manganese electrodes of lithium-ion batteries through coating, dry, roll-in, cut-parts.
2. cathode pole piece is made: according to negative material graphite: acetylene black: LA132=93.5:1.5:5 ratio composite material, and do stirring solvent with distilled water and be modulated into slurry, make anode plate for lithium ionic cell through coating, dry, roll-in, cut-parts.
3. adopt above-mentioned positive and negative electrode pole piece, celgard2400 membrane coil to be coiled into battery, design capacity is 1Ah, and alclad plastic film carries out closedtop, side seal.Electrolyte is 1.5mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, in the glove box that is full of argon gas atmosphere, carry out battery liquid-filling.Take LiMn2O4, conductive agent (acetylene black), conductive agent (Ks-6) binding agent (Kynoar PVDF) according to 94:1:1:4 ratio, slurry modulation evenly, on above-mentioned rich lithium manganese electrodes of lithium-ion batteries, be coated with, the rich lithium manganese electrodes of lithium-ion batteries that improves physical property is made in dry roll-in, cut-parts.Wherein, lithium manganate material accounts for 8.8% of rich lithium manganese and the material modified quality summation of LiMn2O4.
4. battery carries out preliminary filling, changes into.
5. the electric pool gas after changing into is extracted out, heat-sealing, obtains product.
See Fig. 4, this battery is carried out to charge and discharge cycles test: charging/discharging voltage scope is 4.8～2.0V, charging and discharging currents is 0.5A, circulates 100 times, and capability retention is 95.15%, good cycle.Cell thickness has increased by 1.2% than the front thickness of circulation, has no inflatable, improves security performance.
Be understandable that, above execution mode is only used to principle of the present invention is described and the illustrative embodiments that adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (7)
1. a method of improving rich lithium manganese electrodes of lithium-ion batteries physical property, is characterized in that, said method comprising the steps of:
(1), take rich lithium manganese material, conductive agent, binding agent, make solvent with 1-Methyl-2-Pyrrolidone, collector is aluminium foil, slurry modulation evenly, through coating, dryly obtain rich lithium manganese electrodes of lithium-ion batteries;
(2), on the rich lithium manganese electrodes of lithium-ion batteries of preparation, be coated with the material modified slurry of LiFePO4 or LiMn2O4 or the material modified slurry of LiMn2O4, dry, roll-in, cut-parts make the rich lithium manganese electrodes of lithium-ion batteries that improves physical property.
2. method according to claim 1, is characterized in that, in step (1), the mass ratio of rich lithium manganese material, conductive agent, binding agent is 85～96:1～7:3～8; Described conductive agent is acetylene black, Ks-6; Described binding agent is Kynoar.
3. method according to claim 1 and 2, is characterized in that, described rich lithium manganese material is xLi
2mnO
3(1-x) LiMO
2, wherein M is Ni
0.5-y/2mn
0.5-y/2al
y, 0.002≤y≤0.15,0.05≤x≤0.95, particle diameter D50 is 5-15um, tap density is 1.5-2.1g/cm
3.
4. method according to claim 1, it is characterized in that, the preparation method of the material modified slurry of the material modified slurry of LiFePO4 or LiMn2O4 or LiMn2O4 is in step (2), take the material modified or LiMn2O4 of LiFePO4 or LiMn2O4 is material modified, conductive agent, binding agent according to 88～94:3～5:3～7 ratio, slurry modulation evenly, to obtain final product; Described conductive agent acetylene black, Ks-6; Described binding agent is Kynoar.
5. method according to claim 4, is characterized in that, described LiFePO4 is material modified comprises LiFePO4 coated with carbon or/and adulterate, and particle diameter D50 is 0.9-6um, and tap density is 0.9-1.7g/cm
3.
6. method according to claim 4, is characterized in that, described LiMn2O4 or LiMn2O4 are material modified, and wherein LiMn2O4 is material modified comprises LiMn2O4 doping or/and surface is coated, and particle diameter D50 is 5-17um, and tap density is 1.5-2.5g/cm
3.
7. method according to claim 1, it is characterized in that, wherein material modified the or LiMn2O4 of LiFePO4 or lithium manganate material account for the material modified or LiMn2O4 of LiFePO4 on pole piece or LiMn2O4 is material modified and rich lithium manganese material gross mass 0.5%～10%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428642A (en) * | 2015-12-15 | 2016-03-23 | 新余英泰能科技有限公司 | Method for producing energy storage lithium ion battery by using lithium-rich manganese cathode material |
| CN108807980A (en) * | 2018-09-04 | 2018-11-13 | 桑德集团有限公司 | Positive electrode, anode and lithium ion battery |
| CN108987671A (en) * | 2018-08-13 | 2018-12-11 | 北京卫蓝新能源科技有限公司 | A kind of high safety anode composite pole piece, preparation method and its application |
| CN109461882A (en) * | 2018-11-05 | 2019-03-12 | 宁德新能源科技有限公司 | Anode pole piece, electrochemical appliance and the electronic device comprising it |
| CN113241477A (en) * | 2021-05-07 | 2021-08-10 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1658413A (en) * | 2004-02-17 | 2005-08-24 | 比亚迪股份有限公司 | Lithium cell plus plate and its preparation method and lithium ion secondary battery |
| CN103904311A (en) * | 2012-12-28 | 2014-07-02 | 北京有色金属研究总院 | Surface coating and compounding lithium-rich manganese-based positive electrode material and preparation method of positive electrode material |
-
2014
- 2014-09-27 CN CN201410503805.8A patent/CN104201342A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1658413A (en) * | 2004-02-17 | 2005-08-24 | 比亚迪股份有限公司 | Lithium cell plus plate and its preparation method and lithium ion secondary battery |
| CN103904311A (en) * | 2012-12-28 | 2014-07-02 | 北京有色金属研究总院 | Surface coating and compounding lithium-rich manganese-based positive electrode material and preparation method of positive electrode material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428642A (en) * | 2015-12-15 | 2016-03-23 | 新余英泰能科技有限公司 | Method for producing energy storage lithium ion battery by using lithium-rich manganese cathode material |
| CN108987671A (en) * | 2018-08-13 | 2018-12-11 | 北京卫蓝新能源科技有限公司 | A kind of high safety anode composite pole piece, preparation method and its application |
| CN108807980A (en) * | 2018-09-04 | 2018-11-13 | 桑德集团有限公司 | Positive electrode, anode and lithium ion battery |
| CN109461882A (en) * | 2018-11-05 | 2019-03-12 | 宁德新能源科技有限公司 | Anode pole piece, electrochemical appliance and the electronic device comprising it |
| US11177469B2 (en) | 2018-11-05 | 2021-11-16 | Ningde Amperex Technology Limited | Cathode, electrochemical device and electronic device comprising the same |
| CN113675367A (en) * | 2018-11-05 | 2021-11-19 | 宁德新能源科技有限公司 | Positive electrode plate, electrochemical device and electronic device comprising same |
| CN113675367B (en) * | 2018-11-05 | 2023-08-25 | 宁德新能源科技有限公司 | Positive electrode sheet, electrochemical device and electronic device comprising same |
| CN113241477A (en) * | 2021-05-07 | 2021-08-10 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN113241477B (en) * | 2021-05-07 | 2023-02-21 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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