CN102637876B - Lithium battery anode material and method for improving cycle performance of battery - Google Patents
Lithium battery anode material and method for improving cycle performance of battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 239000011858 nanopowder Substances 0.000 claims description 12
- 229910013716 LiNi Inorganic materials 0.000 claims description 10
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000007796 conventional method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011149 active material Substances 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract 1
- 229910052788 barium Inorganic materials 0.000 abstract 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 21
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 229910001290 LiPF6 Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- -1 methyl ethyl Chemical group 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011206 ternary composite Substances 0.000 description 6
- 239000007767 bonding agent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910004493 Li(Ni1/3Co1/3Mn1/3)O2 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012748 LiNi0.5Mn0.3Co0.2O2 Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a lithium battery anode material and a method for improving the cycle performance of a battery, which belong to the field of lithium ion secondary batteries. The method comprises the following steps of: adding a small amount of phosphate of barium into a lithium battery plate taking a nickel-cobalt-manganese ternary compound oxide as an active material, wherein the adding amount is 0.5-2 percent based on the amount of the anode active substance; and performing two charging-discharging processes with controlled current, voltage and temperature on the battery with the additive. Due to the adoption of the method, the cycle performance of the battery is remarkably improved at the voltage of 4.4V, and the cycle performance is remarkably improved at the temperature of 50 DEG C.
Description
Technical field
The present invention relates to field of lithium ion secondary, particularly adopt nickel, cobalt, manganese multi-element composite oxide as the lithium battery of positive electrode active materials.
Background technology
Lithium ion battery is the main power source of the portable type electronic product such as mobile phone, notebook computer, and the small form factor requirements lithium rechargeable battery of these electronic equipments has high power capacity and good cycle performance.The application of current lithium battery on hybrid vehicle (HEV) and electric automobile (EV) increases sharply, and electrokinetic cell requires to have high energy storage density (high energy), and cell operating status is also in higher temperature.
United States Patent (USP) (US20030027048) provides by nickel, cobalt, manganese three control of elements in certain limit, synthesis LiNi
xmn
yco
1-x-yo
2solid solution, the composite oxides of the electrochemical function that is improved, the typical material composition used at present is LiNi
1/3mn
1/3co
1/3o
2and LiNi
0.5mn
0.3co
0.2o
2.With the LiCoO previously used
2compare, nickel-cobalt-manganese ternary composite oxides have very large advantage on cost, and fail safe also improves, and therefore progressively substitute LiCoO
2as one of anode material for lithium-ion batteries.
With nickel-cobalt-manganese ternary composite oxides as positive pole, the battery formed with lithium metal or graphite can be charged to and use higher than 4.2V voltage, and the considerable advantage brought thus to obtain high specific discharge capacity.Obtain discharge capacity 175mAh/g when being charged to 4.4V, and circulation ability compares LiCoO
2much better [N. Yabuuchi, Y. Makamura, T. Ohzuku, Solid state chemistry of Li (Ni
1/3co
1/3mn
1/3) O
2for advanced lithium-ion batteries, J. Electrochem. Soc., 2007,1154:A314-321].Be charged to 4.6V specific discharge capacity even up to 200 mAh/g, but capacity attenuation is still very fast, can not meet application requirement.
Usually organic electrolyte and LiPF6 electrolyte is used in the lithium battery of current use, to use under higher than 4.4V current potential or when using at higher ambient temperatures, transition metal positive active material can accelerate electrolyte decomposition and with electrolytical reaction, cause the change of active material surface solid electrolyte film (SEI) character.During circulating battery, reaction can continue to occur, and battery internal resistance is increased fast, and capacity reduces.The anode material of lithium battery of nickel, cobalt, manganese element composite oxides has higher surface activity, and such as surperficial moisture absorption is high, and reversible capacity only has 87% usually first, far below cobalt acid lithium.In nickel-cobalt-manganese ternary composite oxides, add some element can improve circulation volume hold facility, such as add a small amount of Mg or F and have better effects [H-S. Shin, D. Shin, Y-K. Sun, Improvement of electrochemical properties of Li [Ni
0.4co
0.2mn
(0.4-x)mg
x] O
2-yf
ycathode materials at high voltage region, Electrochimica Acta, 2006,52:1477.].Current another kind of solution in organic electrolyte, adds stabilizer to reduce electrolyte decomposition, and patent [CN201010273555.5] discloses adds the fine method of second two in the electrolytic solution.
It is more than prior art.
The preparation method of positive plate of lithium battery in prior art:
(1) metal tripolyphosphate nano powder is added in solvent according to solid-to-liquid ratio (g/ml) 0.5 ~ 2:100, fully stir and make nano-powder dispersion, obtain mixture (adopting ultrasonic disperse can reach very good effect in more than 15 minutes);
(2) conductive agent dried is in advance added in above mixture according to 4 ~ 6wt% of active material, again the bonding agent of active material 2 ~ 5wt% is dissolved in a solvent, then the solution dissolving bonding agent is added in mixture, finally mixture is fully stirred 15 ~ 30 minutes, make it mix;
(3) added by battery anode active material in the mixture obtained in step (2), the viscosity adding the mixed slurry of solvent adjustment makes it to be convenient to coating, then stirs and obtains mixed slurry in 60 ~ 90 minutes;
(4) slurry even application will be mixed on aluminium foil (collector electrode), then 120 DEG C of bakings 8 ~ 12 hours, obtain the lithium battery anode be coated on collector electrode; As the compacted density of pole piece material need be improved, roller process can be carried out.
Described metal tripolyphosphate nano powder is Ba
3(PO
4)
2, purity is more than 99.9wt%.
Described solvent is any one in absolute ethyl alcohol, acetone or NMP, is common commercially available.Consider to coordinate with follow-up Fabrication Technology of Electrode, usually adopt NMP to be solvent.
Described conductive agent is carbon black, for common commercially available.Conductive agent needs before use 120 DEG C of dryings.
Described bonding agent is PVDF.
Described cell positive material is nickel-cobalt-manganese ternary oxide material.The aerial nickel-cobalt-manganese ternary oxide material of long-time exposure needs to toast more than 4 hours at 150 DEG C before use.
Advantage of the present invention and good effect:
By adding phosphate in positive plate, and coordinating two charge and discharge process, being conducive to generating uniformly at nickel-cobalt-manganese ternary complex oxide surface, stablizing SEI film, stoping the further decomposition of electrolyte.The advantage so obtaining battery is as positive pole with nickel-cobalt-manganese ternary composite oxides, stable performance during the battery formed with graphite can be charged to and use higher than 4.2V voltage, the considerable advantage brought thus to obtain high specific discharge capacity, such as, obtain discharge capacity 176mAh/g when being charged to 4.4V, be charged to 4.6V specific discharge capacity even up to 194 mAh/g.
Another advantage is, nickel-cobalt-manganese ternary composite oxides are as positive pole, and the battery formed with graphite can use at relatively high temperatures and still have high capacity hold facility.Such as circulate at the temperature of 50 DEG C, battery can reach the conservation rate of more than 97%.When unstable process, battery can only reach the conservation rate of 85%, and therefore the present invention uses capacity attenuation problem faster under solving higher temperature, meets electrokinetic cell application requirement.
Summary of the invention
The invention provides a kind of method of anode material of lithium battery and raising cycle performance of battery, the problem solved improves the capacity hold facility of cobalt nickel oxide manganses lithium as the lithium rechargeable battery of positive pole, especially higher than the job stability under 4.2V current potential, reduce the decomposition of organic electrolyte at electrode surface, make battery have high power capacity and increase useful life, another object improves battery in the stability higher than 50 DEG C of circulation times, thus a kind of method improving cycle performance of lithium ion battery proposed.
The scheme that the present invention adopts is that the battery that lithium battery material forms is carried out pre-charge and discharge process.Anode material of lithium battery is coated in collector electrode comprises positive active material and phosphatic mixture.Phosphate is 0.5 ~ 2wt% of positive active material.
Described positive active material is cobalt nickel oxide manganses lithium, has layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein 0.15≤x≤0.3,0.2≤y≤0.4.
The described phosphate added when preparing battery anode slice is Ba
3(PO
4)
2nano powder, purity is more than 99.9wt%.The particles benefit of refinement additive is in reaching above-mentioned effect, and therefore this programme is paid the utmost attention to and adopted nanoscale barium phosphate, determines that impurity is removed, and ensures that nano particle can effectively disperse.
The battery that described lithium ion anode sheet is assembled is carried out discharge and recharge by the present invention, makes electrode material surface can generate stable solid electrolyte film (SEI film), thus improve battery follow-up use time capacity hold facility.Add phosphate in electrode to contribute to forming uniform and stable SEI film in preliminary filling discharge process, thus battery can be charged to higher than 4.2V voltage in follow-up use, or the cycle performance that still can keep when using higher than room temperature.Concrete steps include down:
(1) anode material for lithium-ion batteries is assembled into battery, carries out first time discharge and recharge: place 12 hours under the condition of 45 ~ 50 DEG C, then with 0.4 ~ 0.6C current charges to 3.8 ~ 4.0V, to stop after 10 minutes, then with 0.4 ~ 0.6C current discharge to 3.0V;
(2) second time discharge and recharge is carried out after first time discharge and recharge: placed more than 6 hours under the condition of room temperature 20 ~ 25 DEG C by battery, then with 0.1 ~ 0.2C current charges to 4.2V, stop 10 minutes, then with 0.1 ~ 0.2C current discharge to 2.75V, the lithium battery after the cycle performance that is finally improved.
Positive electrode of the present invention is coated on collector electrode, can be assembled into battery with graphite or other negative material, also directly can do negative pole assembled battery with lithium paper tinsel.The electrolyte of battery is not limited, conventional organic electrolyte and LiPF in lithium battery can be used
6electrolyte.
First time discharge and recharge need be carried out at the temperature of 40 ~ 50 DEG C, adopts higher temperature to be conducive to the infiltration of electrolyte and electrode active material, improves ion mobility.The charge-discharge velocity of employing 0.4 ~ 0.6C can Reaction time shorten.Because various ion diffusion rate is in the electrolytic solution different, so the main body of carrying out electrochemical reaction under large current density is just not identical with during low current density, the composition of the SEI film obtained is also different.Under high current density, inorganic ions transport number is comparatively large, and inorganic component has higher ratio.Above process helps is in the SEI film phosphate be added in advance in anode pole piece being attached to active material surface generation.
In first time charge and discharge process, have employed higher temperature and larger current density, the SEI film obtained like this has more pore structure, usually also stable not.Such battery comes into operation immediately, SEI film by continued propagation, until have enough thickness and compactness.Therefore also to control second time charge and discharge process before the use, adopt low temperature and carrying out with 0.1 ~ 0.2C low current density, decompose because small area analysis is conducive to organic component in electrolyte, and fill SEI membrane pores and make it have stable thickness and density.
Embodiment
Below by embodiment, the present invention is described in further detail, but the invention is not restricted to following protection range.
The preparation method of positive plate of lithium battery in following examples:
(1) metal tripolyphosphate nano powder is added in solvent according to solid-to-liquid ratio (g/ml) 0.5 ~ 2:100, fully stir and make nano-powder dispersion, obtain mixture (adopting ultrasonic disperse can reach very good effect in more than 15 minutes);
(2) conductive agent dried is in advance added in above mixture according to 4 ~ 6wt% of active material, again the bonding agent of active material 2 ~ 5wt% is dissolved in a solvent, then the solution dissolving bonding agent is added in mixture, finally mixture is fully stirred 15 ~ 30 minutes, make it mix;
(3) added by battery anode active material in the mixture obtained in step (2), the viscosity adding the mixed slurry of solvent adjustment makes it to be convenient to coating, then stirs and obtains mixed slurry in 60 ~ 90 minutes;
(4) slurry even application will be mixed on aluminium foil (collector electrode), then 120 DEG C of bakings 8 ~ 12 hours, obtain the lithium battery anode be coated on collector electrode; As the compacted density of pole piece material need be improved, roller process can be carried out.
Embodiment 1: the anode material of lithium battery that the present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in lithium battery anode is the 2wt% of positive active material.Positive active material is cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein x=0.15, y=0.4.Phosphate is Ba
3(PO
4)
2nano powder, purity is more than 99.9wt%.
Positive plate is cut into the disk of diameter 12 millimeters, makes negative pole assembling button cell with lithium paper tinsel.Select the lithium battery electrolytes of mixing, proportioning is EC:DEC:DMC(diethyl carbonate: dimethyl carbonate: methyl ethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L.
(1) battery assembled is carried out first time discharge and recharge: place 12 hours under the condition of 45 DEG C, then with 0.4C current charges to 4.0V, to stop after 10 minutes, then with 0.4C current discharge to 3.0V;
(2) second time discharge and recharge is carried out after first time discharge and recharge, battery is placed more than 6 hours under the condition of 18 DEG C, then with 0.2C current charges to 4.2V, stop 10 minutes, again with 0.1C current discharge to 2.75V, the lithium battery after the cycle performance that is finally improved.
Embodiment 2: the anode material of lithium battery that the present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in lithium battery anode is the 1wt% of positive active material.Positive active material is cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein x=0.2, y=0.3.Phosphate is Ba
3(PO
4)
2nano powder, purity is more than 99.9wt%.
Positive plate is cut into the disk of diameter 12 millimeters, makes negative pole assembling button cell with lithium paper tinsel.Select the lithium battery electrolytes of mixing, proportioning is EC:DEC:DMC(diethyl carbonate: dimethyl carbonate: methyl ethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L.
(1) lithium ion cell positive adding phosphate lithium is assembled into battery, carries out first time discharge and recharge: place 12 hours under the condition of 48 DEG C, then with 0.5C current charges to 3.8V, to stop after 10 minutes, then with 0.5C current discharge to 3.0V;
(2) second time discharge and recharge is carried out after first time discharge and recharge, battery is placed more than 6 hours under the condition of 20 DEG C, then with 0.1C current charges to 4.2V, stop 10 minutes, again with 0.15C current discharge to 2.75V, the lithium battery after the cycle performance that is finally improved.
Embodiment 3: the anode material of lithium battery that the present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in lithium battery anode is the 0.5wt% of positive active material.Positive active material is cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein x=0.3, y=0.2.Phosphate is Ba
3(PO
4)
2nano powder, purity is more than 99.9wt%.
Positive plate is cut into the disk of diameter 12 millimeters, makes negative pole assembling button cell with lithium paper tinsel.Select the lithium battery electrolytes of mixing, proportioning is EC:DEC:DMC(diethyl carbonate: dimethyl carbonate: methyl ethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L.
(1) lithium ion cell positive adding phosphate lithium is assembled into battery, carries out first time discharge and recharge: place 12 hours under the condition of 50 DEG C, then with 0.6C current charges to 3.9V, to stop after 10 minutes, then with 0.6C current discharge to 3.0V;
(2) second time discharge and recharge is carried out after first time discharge and recharge, battery is placed more than 6 hours under the condition of 25 DEG C, then with 0.15C current charges to 4.2V, stop 10 minutes, again with 0.2C current discharge to 2.75V, the lithium battery after the cycle performance that is finally improved.
Embodiment 4: the anode material of lithium battery that the present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in lithium battery anode is the 1wt% of positive active material.Positive active material is cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein x=0.25, y=0.35.Phosphate is Ba
3(PO
4)
2nano powder, purity is more than 99.9wt%.
Positive plate is cut into the disk of diameter 12 millimeters, makes negative pole assembling button cell with lithium paper tinsel.Select the lithium battery electrolytes of mixing, proportioning is EC:DEC:DMC(diethyl carbonate: dimethyl carbonate: methyl ethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L.
(1) lithium ion cell positive adding phosphate lithium is assembled into battery, carries out first time discharge and recharge: place 12 hours under the condition of 46 DEG C, then with 0.4C current charges to 3.8V, to stop after 10 minutes, then with 0.6C current discharge to 3.0V;
(2) second time discharge and recharge is carried out after first time discharge and recharge, battery is placed more than 6 hours under the condition of 22 DEG C, then with 0.2C current charges to 4.2V, stop 10 minutes, again with 0.2C current discharge to 2.75V, the lithium battery after the cycle performance that is finally improved.
Comparative example 1: the anode material of lithium battery that the present embodiment adopts mainly is made up of positive active material.Described positive active material is cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein x=0.25, y=0.35.Positive plate is cut into the disk of diameter 12 millimeters, makes negative pole assembling button cell with lithium paper tinsel.Select the lithium battery electrolytes of mixing, proportioning is EC:DEC:DMC(diethyl carbonate: dimethyl carbonate: methyl ethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L.Consistent with the charge and discharge process of embodiment 1 after being assembled into battery.
Comparative example 2: the present embodiment adopts anode material of lithium battery to be mainly made up of positive active material.Positive active material is nickel-cobalt-manganese ternary composite oxides, layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein x=0.2, y=0.4.Positive plate is cut into the disk of diameter 12 millimeters, makes negative pole assembling button cell with lithium paper tinsel.Select the lithium battery electrolytes of mixing, proportioning is EC:DEC:DMC(diethyl carbonate: dimethyl carbonate: methyl ethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L.Consistent with the charge and discharge process of embodiment 1 after being assembled into battery.
Cycle performance is tested: by embodiment 1 ~ 4, under the battery different temperatures of the positive plate of comparative example 1 ~ 2 assembling with 28mA/g current charges to 4.4V, stop 10 minutes, then with 28mA/g current discharge to 2.75V, now obtain 0.2C discharge capacity.Repeat this cyclic process 50 times.Result is charged in table 1.
The amount of table 1 additive and test result
Embodiment 5: consistent with described in embodiment 1 of anode material of lithium battery and battery charge and discharge process that this enforcement adopts.
Embodiment 6: consistent with described in embodiment 2 of anode material of lithium battery and battery charge and discharge process that this enforcement adopts.
Embodiment 7: consistent with described in embodiment 3 of anode material of lithium battery and battery charge and discharge process that this enforcement adopts.
Embodiment 8: the anode material of lithium battery that the present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in lithium battery anode is the 1wt% of positive active material.Positive active material is cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yco
xmn
yo
2, wherein x=0.2, y=0.3.Phosphate is Ba
3(PO
4)
2nano powder, purity is more than 99.9wt%.Positive plate is cut into the disk of diameter 12 millimeters, makes negative pole assembling button cell with lithium paper tinsel.Select the lithium battery electrolytes of mixing, proportioning is EC:DEC:DMC(diethyl carbonate: dimethyl carbonate: methyl ethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L.Consistent with the charge and discharge process of embodiment 2 after being assembled into battery.
Comparative example 3: consistent with the cell positive material of comparative example 1 and battery charge and discharge process.
The test of cycle performance: by embodiment 5 ~ 8, comparative example 3 positive electrode assembling battery at 50 DEG C of temperature with 28mA/g current charges to 4.2V, stop 10 minutes, then with 28mA/g current discharge to 2.75V, now obtain 0.2C discharge capacity.Repeat this cyclic process 50 times.Capacity keeps the results are shown in table 2.
The capacity of the amount of table 2 additive and 50 circulations keeps
Claims (1)
1. improve a method for the cycle performance of battery of anode material of lithium battery composition, anode material of lithium battery comprises positive active material and phosphatic mixture, and described positive active material is cobalt nickel oxide manganses lithium, layered crystal structure, and chemical formula is LiNi
1-x-yco
xmn
yo
2, wherein 0.15≤x≤0.3,0.2≤y≤0.4, described phosphate is Ba
3(PO
4)
2nano powder, purity is more than 99.9wt%, and the phosphate content in described anode material of lithium battery is 0.5 ~ 2wt% of positive active material, it is characterized in that concrete steps comprise as follows:
(1) anode material of lithium battery is assembled into battery according to a conventional method, carry out first time discharge and recharge: place 12 hours under the condition of 45 DEG C ~ 50 DEG C, then with 0.4C ~ 0.6C current charges to 3.8V ~ 4.0V, to stop after 10 minutes, then with 0.4 ~ 0.6C current discharge to 3.0V;
(2) second time discharge and recharge is carried out after first time discharge and recharge: battery is placed more than 6 hours under the condition of 18 ~ 25 DEG C, then with 0.1 ~ 0.2C current charges to 4.2V, stop 10 minutes, again with 0.1 ~ 0.2C current discharge to 2.75V, the battery of anode material of lithium battery after the cycle performance that is finally improved composition.
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