CN102637876A - 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
- Publication number
- CN102637876A CN102637876A CN2012101368416A CN201210136841A CN102637876A CN 102637876 A CN102637876 A CN 102637876A CN 2012101368416 A CN2012101368416 A CN 2012101368416A CN 201210136841 A CN201210136841 A CN 201210136841A CN 102637876 A CN102637876 A CN 102637876A
- Authority
- CN
- China
- Prior art keywords
- battery
- lithium battery
- lithium
- anode material
- cycle performance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010405 anode material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- 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
- 238000007599 discharging Methods 0.000 claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 18
- 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 18
- 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
- 239000003792 electrolyte Substances 0.000 description 23
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 14
- 239000011572 manganese Substances 0.000 description 12
- 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
- 238000002156 mixing Methods 0.000 description 7
- AHIHJODVQGBOND-UHFFFAOYSA-N propan-2-yl hydrogen carbonate Chemical compound CC(C)OC(O)=O AHIHJODVQGBOND-UHFFFAOYSA-N 0.000 description 7
- 239000011206 ternary composite Substances 0.000 description 7
- 229910000497 Amalgam Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007767 bonding agent Substances 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 238000002360 preparation method Methods 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
- 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
- 125000004122 cyclic group Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011049 filling 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
- 239000011148 porous material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 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
- 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
- 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
- 238000005516 engineering process 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 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 multielement composite oxides lithium battery as positive electrode active materials.
Background technology
Lithium ion battery is the main power supply of portable type electronic products such as mobile phone, notebook computer, and the miniaturization of these electronic equipments requires lithium rechargeable battery to have high power capacity and excellent cycle performance.The application of lithium battery on hybrid vehicle (HEV) and electric automobile (EV) at present increases sharply, and electrokinetic cell requires to have high energy storage density (high energy), and battery operated state also is in higher temperature.
United States Patent (USP) (US20030027048) provides nickel, cobalt, three elements of manganese is controlled at certain limit, synthetic LiNi
xMn
yCo
1-x-yO
2Solid solution, the composite oxides of the electrochemical function that is improved, the typical material composition that uses at present is LiNi
1/3Mn
1/3Co
1/3O
2And LiNi
0.5Mn
0.3Co
0.2O
2LiCoO with previous use
2Compare, the nickel-cobalt-manganese ternary composite oxides have very big advantage on cost, and fail safe also improves, and therefore progressively substitute LiCoO
2As one of anode material for lithium-ion batteries.
As positive pole, the battery of forming with lithium metal or graphite can be charged to and be higher than 4.2V voltage and use with the nickel-cobalt-manganese ternary composite oxides, and the considerable advantage that brings thus is 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 the 4.6V specific discharge capacity even up to 200 mAh/g, but capacity attenuation is still very fast, can not satisfy application requirements.
Usually use organic electrolyte and LiPF6 electrolyte in the lithium battery that uses at present; Use or than high ambient temperature under during use being higher than under the 4.4V current potential; The transition metal positive active material can quicken electrolyte decomposition and with electrolytical reaction, cause the change of active material surface solid electrolyte film (SEI) character.The reaction of battery circulation time can continue to take place, 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 for example surperficial moisture absorption is high, and reversible capacity has only 87% usually first, far below cobalt acid lithium.In the nickel-cobalt-manganese ternary composite oxides, add some element and can improve the circulation volume hold facility; For example add a small amount of Mg or F better effects [H-S. Shin is arranged; 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.].Present another kind of solution is in organic electrolyte, to add stabilizer to reduce electrolyte decomposition, and patent [CN201010273555.5] discloses adds the fine method of second two in electrolyte.
It more than is prior art.
Summary of the invention
The present invention provides a kind of anode material of lithium battery and improves the method for cycle performance of battery; The problem that solves is to improve the capacity hold facility of cobalt nickel oxide manganses lithium as the lithium rechargeable battery of positive pole; Especially at the job stability that is higher than under the 4.2V current potential; Reduce the decomposition of organic electrolyte at electrode surface; Make battery have high power capacity and increase useful life, another purpose is to improve battery in the stability that is higher than 50 ℃ of circulation times, thus a kind of method that improves the lithium ion battery cycle performance that proposes.
The scheme that the present invention adopts is that the battery that lithium battery material is formed is carried out the preliminary filling discharge process.Anode material of lithium battery is to be coated in to comprise positive active material and phosphatic mixture on the collector electrode.Phosphate is 0.5～2wt% of positive active material.
Said positive active material is the cobalt nickel oxide manganses lithium, has layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, 0.15≤x≤0.3,0.2≤y≤0.4 wherein.
The phosphate that adds during said preparation battery anode slice is Ba
3(PO
4)
2Nano powder, purity are more than the 99.9wt%.The particle of refinement additive helps reaching above-mentioned effect, so this programme pays the utmost attention to and adopt the nanoscale barium phosphate, confirms that impurity removes, and guarantees that nano particle can effectively disperse.
The present invention discharges and recharges the battery of described lithium ion anode sheet assembling, makes electrode material surface can generate stable solid dielectric film (SEI film), thereby improves the capacity hold facility when battery is follow-up to be used.Add phosphate in the electrode and in the preliminary filling discharge process, help to form uniform and stable SEI film, thereby battery can be charged in follow-up use and be higher than 4.2V voltage, perhaps still can keep good cycle performance when room temperature is used being higher than.Concrete steps include down:
(1) anode material for lithium-ion batteries is assembled into battery, carries out discharging and recharging for the first time: 45 ~ 50 ℃ condition held 12 hours,, stop after 10 minutes then with 0.4 ~ 0.6C current charges to 3.8 ~ 4.0V, again with 0.4 ~ 0.6C current discharge to 3.0V;
(2) carry out discharging and recharging for the second time after discharging and recharging for the first time: with battery in the condition held of 20 ~ 25 ℃ of room temperatures more than 6 hours; Arrive 4.2V with 0.1 ~ 0.2C current charges then; Stopped 10 minutes, again with 0.1 ~ 0.2C current discharge to 2.75V, the lithium battery behind the cycle performance that finally is improved.
Positive electrode of the present invention is coated on the collector electrode, can be assembled into battery with graphite or other negative material, also can directly do negative pole assembled battery with the lithium paper tinsel.Electrolyte to battery is unqualified, can use organic electrolyte commonly used and LiPF in the lithium battery
6Electrolyte.
Discharging and recharging for the first time needs under 40～50 ℃ temperature, to carry out, and adopts higher temperature to help the infiltration of electrolyte and electrode active material, improves the ion migration rate.Adopt the charge-discharge velocity of 0.4～0.6C to shorten the reaction time.Because the diffusion rate of various ions in electrolyte is different, so the main body of under big current density, carrying out electrochemical reaction is inequality during just with low current density, the composition of the SEI film that obtains is difference also.The inorganic ions transport number is bigger under the high current density, and inorganic component has higher ratio.Above process helps the phosphate that is added in advance in the anode pole piece is attached in the SEI film of active material surface generation.
Adopted higher temperature and bigger current density in the charge and discharge process in the first time, the SEI film that obtains like this has more pore structure, and is also stable inadequately usually.Such battery comes into operation immediately, and the SEI film will continue growth, up to enough thickness and compactness are arranged.Therefore before using, also to control charge and discharge process for the second time, adopt low temperature and carry out,, and fill the SEI membrane pores and make it have stable thickness and density because little electric current helps that organic component decomposes in the electrolyte with 0.1～0.2C low current density.
The preparation method of lithium battery anode sheet in the prior art:
(1) the metal tripolyphosphate nano powder is added in the solvent according to solid-to-liquid ratio (g/ml) 0.5～2:100, fully stir and make the nano powder dispersion, obtain amalgam (adopting ultrasonic dispersion can reach very good effect more than 15 minutes);
(2) the dry in advance conductive agent of crossing of general adds in the above amalgam according to 4～6wt% of active material; Bonding agent with active material 2～5wt% is dissolved in the solvent again; The solution that will dissolve bonding agent then adds in the amalgam; At last mixture was fully stirred 15～30 minutes, it is mixed;
(3) battery anode active material is added in the mixture that obtains in the step (2), the viscosity that adds the mixed slurry of solvent adjustment makes it to be convenient to apply, and stirs then and obtains mixed slurry in 60～90 minutes;
(4) will mix slurry and evenly be coated on the aluminium foil (collector electrode), 120 ℃ of bakings 8～12 hours, obtain being coated in the lithium battery anode on the collector electrode then; Like the compacted density of need raising pole piece material, can carry out roller process.
Said metal tripolyphosphate nano powder is Ba
3(PO
4)
2, purity is more than the 99.9wt%.
Said solvent is any one among absolute ethyl alcohol, acetone or the NMP, is common commercially available.Consider to cooperate with follow-up electrode manufacture craft, adopting NMP usually is solvent.
Said conductive agent is a carbon black, for common commercially available.Conductive agent before use need be 120 ℃ of dryings.
Said bonding agent is PVDF.
Said cell positive material is the nickel-cobalt-manganese ternary oxide material.Being exposed to airborne nickel-cobalt-manganese ternary oxide material for a long time need toast more than 4 hours down at 150 ℃ before use.
Advantage of the present invention and good effect:
Through in positive plate, adding phosphate, and cooperate two charge and discharge process, help generating uniformly, stablize SEI film, the further decomposition of prevention electrolyte on nickel-cobalt-manganese ternary composite oxides surface.The advantage that so obtains battery is as positive pole with the nickel-cobalt-manganese ternary composite oxides; The battery of forming with graphite can be charged to be higher than 4.2V voltage use in stable performance; The considerable advantage that brings thus is to obtain high specific discharge capacity; Obtain discharge capacity 176mAh/g when for example being charged to 4.4V, be charged to the 4.6V specific discharge capacity even up to 194 mAh/g.
Another advantage is, the nickel-cobalt-manganese ternary composite oxides are as positive pole, and the battery of forming with graphite can use under higher temperature and still have high capacity hold facility.For example under 50 ℃ temperature, circulate, battery can reach the conservation rate more than 97%.Do not having under the situation of stabilized treatment, battery can only reach 85% conservation rate, so the present invention solves under the higher temperature and to use capacity attenuation problem faster, satisfies the electrokinetic cell application requirements.
Embodiment
Through embodiment the present invention is done further detailed description below, but the invention is not restricted to following protection range.
The preparation method of lithium battery anode sheet in following examples:
(1) the metal tripolyphosphate nano powder is added in the solvent according to solid-to-liquid ratio (g/ml) 0.5～2:100, fully stir and make the nano powder dispersion, obtain amalgam (adopting ultrasonic dispersion can reach very good effect more than 15 minutes);
(2) the dry in advance conductive agent of crossing of general adds in the above amalgam according to 4～6wt% of active material; Bonding agent with active material 2～5wt% is dissolved in the solvent again; The solution that will dissolve bonding agent then adds in the amalgam; At last mixture was fully stirred 15～30 minutes, it is mixed;
(3) battery anode active material is added in the mixture that obtains in the step (2), the viscosity that adds the mixed slurry of solvent adjustment makes it to be convenient to apply, and stirs then and obtains mixed slurry in 60～90 minutes;
(4) will mix slurry and evenly be coated on the aluminium foil (collector electrode), 120 ℃ of bakings 8～12 hours, obtain being coated in the lithium battery anode on the collector electrode then; Like the compacted density of need raising pole piece material, can carry out roller process.
Embodiment 1: the anode material of lithium battery that present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in the lithium battery anode is the 2wt% of positive active material.Positive active material is the cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, x=0.15 wherein, y=0.4.Phosphate is Ba
3(PO
4)
2Nano powder, purity are more than the 99.9wt%.
Positive plate is cut into the disk of 12 millimeters of diameters, makes negative pole assembling button cell with the lithium paper tinsel.Select the lithium battery electrolytes of mixing for use, proportioning is that (diethyl carbonate: dimethyl carbonate: carbonic acid Methylethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L to EC:DEC:DMC.
(1) battery that assembles is carried out discharging and recharging for the first time: 45 ℃ condition held 12 hours, then with the 0.4C current charges to 4.0V, stop after 10 minutes, again with the 0.4C current discharge to 3.0V;
(2) carry out discharging and recharging the second time after discharging and recharging for the first time; With battery 18 ℃ condition held more than 6 hours, then with the 0.2C current charges to 4.2V, stopped 10 minutes; Again with the 0.1C current discharge to 2.75V, the lithium battery behind the cycle performance that finally is improved.
Embodiment 2: the anode material of lithium battery that present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in the lithium battery anode is the 1wt% of positive active material.Positive active material is the cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, x=0.2 wherein, y=0.3.Phosphate is Ba
3(PO
4)
2Nano powder, purity are more than the 99.9wt%.
Positive plate is cut into the disk of 12 millimeters of diameters, makes negative pole assembling button cell with the lithium paper tinsel.Select the lithium battery electrolytes of mixing for use, proportioning is that (diethyl carbonate: dimethyl carbonate: carbonic acid Methylethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L to EC:DEC:DMC.
(1) lithium ion cell positive that adds the phosphate lithium is assembled into battery, carries out discharging and recharging for the first time: 48 ℃ condition held 12 hours, then with the 0.5C current charges to 3.8V, stop after 10 minutes, again with the 0.5C current discharge to 3.0V;
(2) carry out discharging and recharging the second time after discharging and recharging for the first time; With battery 20 ℃ condition held more than 6 hours, then with the 0.1C current charges to 4.2V, stopped 10 minutes; Again with the 0.15C current discharge to 2.75V, the lithium battery behind the cycle performance that finally is improved.
Embodiment 3: the anode material of lithium battery that present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in the lithium battery anode is the 0.5wt% of positive active material.Positive active material is the cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, x=0.3 wherein, y=0.2.Phosphate is Ba
3(PO
4)
2Nano powder, purity are more than the 99.9wt%.
Positive plate is cut into the disk of 12 millimeters of diameters, makes negative pole assembling button cell with the lithium paper tinsel.Select the lithium battery electrolytes of mixing for use, proportioning is that (diethyl carbonate: dimethyl carbonate: carbonic acid Methylethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L to EC:DEC:DMC.
(1) lithium ion cell positive that adds the phosphate lithium is assembled into battery, carries out discharging and recharging for the first time: 50 ℃ condition held 12 hours, then with the 0.6C current charges to 3.9V, stop after 10 minutes, again with the 0.6C current discharge to 3.0V;
(2) carry out discharging and recharging the second time after discharging and recharging for the first time; With battery 25 ℃ condition held more than 6 hours, then with the 0.15C current charges to 4.2V, stopped 10 minutes; Again with the 0.2C current discharge to 2.75V, the lithium battery behind the cycle performance that finally is improved.
Embodiment 4: the anode material of lithium battery that present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in the lithium battery anode is the 1wt% of positive active material.Positive active material is the cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, x=0.25 wherein, y=0.35.Phosphate is Ba
3(PO
4)
2Nano powder, purity are more than the 99.9wt%.
Positive plate is cut into the disk of 12 millimeters of diameters, makes negative pole assembling button cell with the lithium paper tinsel.Select the lithium battery electrolytes of mixing for use, proportioning is that (diethyl carbonate: dimethyl carbonate: carbonic acid Methylethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L to EC:DEC:DMC.
(1) lithium ion cell positive that adds the phosphate lithium is assembled into battery, carries out discharging and recharging for the first time: 46 ℃ condition held 12 hours, then with the 0.4C current charges to 3.8V, stop after 10 minutes, again with the 0.6C current discharge to 3.0V;
(2) carry out discharging and recharging the second time after discharging and recharging for the first time; With battery 22 ℃ condition held more than 6 hours, then with the 0.2C current charges to 4.2V, stopped 10 minutes; Again with the 0.2C current discharge to 2.75V, the lithium battery behind the cycle performance that finally is improved.
Comparative Examples 1: the anode material of lithium battery that present embodiment adopts mainly is made up of positive active material.Said positive active material is the cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, x=0.25 wherein, y=0.35.Positive plate is cut into the disk of 12 millimeters of diameters, makes negative pole assembling button cell with the lithium paper tinsel.Select the lithium battery electrolytes of mixing for use, proportioning is that (diethyl carbonate: dimethyl carbonate: carbonic acid Methylethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L to EC:DEC:DMC.Be assembled into behind the battery consistent with the charge and discharge process of embodiment 1.
Comparative Examples 2: present embodiment adopts anode material of lithium battery mainly to be made up of positive active material.Positive active material is the nickel-cobalt-manganese ternary composite oxides, layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, x=0.2 wherein, y=0.4.Positive plate is cut into the disk of 12 millimeters of diameters, makes negative pole assembling button cell with the lithium paper tinsel.Select the lithium battery electrolytes of mixing for use, proportioning is that (diethyl carbonate: dimethyl carbonate: carbonic acid Methylethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L to EC:DEC:DMC.Be assembled into behind the battery consistent with the charge and discharge process of embodiment 1.
Cycle performance test: with embodiment 1～4, under the battery different temperatures of the positive plate of Comparative Examples 1～2 assembling with the 28mA/g current charges to 4.4V, stopped 10 minutes, again with the 28mA/g current discharge to 2.75V, obtain the 0.2C discharge capacity at this moment.Repeat this cyclic process 50 times.The result charges in the table 1.
The amount of table 1 additive and test result
Embodiment 5: the anode material of lithium battery that this enforcement is adopted is described consistent with embodiment 1 with battery charge and discharge process.
Embodiment 6: the anode material of lithium battery that this enforcement is adopted is described consistent with embodiment 2 with battery charge and discharge process.
Embodiment 7: the anode material of lithium battery that this enforcement is adopted is described consistent with embodiment 3 with battery charge and discharge process.
Embodiment 8: the anode material of lithium battery that present embodiment adopts mainly is made up of positive active material and phosphate.Phosphate content in the lithium battery anode is the 1wt% of positive active material.Positive active material is the cobalt nickel oxide manganses lithium, layered crystal structure, chemical composition LiNi
1-x-yCo
xMn
yO
2, x=0.2 wherein, y=0.3.Phosphate is Ba
3(PO
4)
2Nano powder, purity are more than the 99.9wt%.Positive plate is cut into the disk of 12 millimeters of diameters, makes negative pole assembling button cell with the lithium paper tinsel.Select the lithium battery electrolytes of mixing for use, proportioning is that (diethyl carbonate: dimethyl carbonate: carbonic acid Methylethyl ester) be 1:1:1, electrolyte is the LiPF6 of 1mol/L to EC:DEC:DMC.Be assembled into behind the battery consistent with the charge and discharge process of embodiment 2.
Comparative Examples 3: consistent with the cell positive material and the battery charge and discharge process of Comparative Examples 1.
The test of cycle performance: with embodiment 5～8, the battery of the positive electrode of Comparative Examples 3 assembling under 50 ℃ of temperature with the 28mA/g current charges to 4.2V, stopped 10 minutes, again with the 28mA/g current discharge to 2.75V, obtain the 0.2C discharge capacity at this moment.Repeat this cyclic process 50 times.Capacity keeps the result to be listed in the table 2.
The capacity of the amount of table 2 additive and 50 circulations keeps
Claims (5)
1. anode material of lithium battery, it is characterized in that: anode material of lithium battery is to comprise positive active material and phosphatic mixture.
2. anode material of lithium battery according to claim 1 is characterized in that: the phosphate content in the said anode material of lithium battery is 0.5～2wt% of positive active material.
3. anode material of lithium battery according to claim 1 is characterized in that: said positive active material is the cobalt nickel oxide manganses lithium, and layered crystal structure, chemical formula are LiNi
1-x-yCo
xMn
yO
2, 0.15≤x≤0.3,0.2≤y≤0.4 wherein.
4. anode material of lithium battery according to claim 1 is characterized in that: said phosphate is Ba
3(PO
4)
2Nano powder, purity are more than the 99.9wt%.
5. method that improves the cycle performance of battery that the described anode material of lithium battery of claim 1 forms is characterized in that concrete steps comprise as follows:
(1) anode material of lithium battery is assembled into battery by conventional method; Carry out discharging and recharging for the first time: 45 ℃～50 ℃ condition held 12 hours; Then with 0.4C～0.6C current charges to 3.8V～4.0V, stop after 10 minutes, again with 0.4～0.6C current discharge to 3.0V;
(2) carry out discharging and recharging for the second time after discharging and recharging for the first time: battery is 18～25 ℃ condition held more than 6 hours; Arrive 4.2V with 0.1～0.2C current charges then; Stopped 10 minutes; Again with 0.1～0.2C current discharge to 2.75V, the battery that anode material of lithium battery behind the cycle performance that finally is improved is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210136841.6A CN102637876B (en) | 2012-05-07 | 2012-05-07 | Lithium battery anode material and method for improving cycle performance of battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210136841.6A CN102637876B (en) | 2012-05-07 | 2012-05-07 | Lithium battery anode material and method for improving cycle performance of battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102637876A true CN102637876A (en) | 2012-08-15 |
| CN102637876B CN102637876B (en) | 2014-12-31 |
Family
ID=46622183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210136841.6A Expired - Fee Related CN102637876B (en) | 2012-05-07 | 2012-05-07 | Lithium battery anode material and method for improving cycle performance of battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102637876B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104577203A (en) * | 2014-05-21 | 2015-04-29 | 深圳市格瑞普电池有限公司 | Preparation method of lithium ion battery |
| CN106058224A (en) * | 2016-08-19 | 2016-10-26 | 周新凤 | Composite lithium battery cathode material and preparation method thereof |
| CN111384458A (en) * | 2019-12-25 | 2020-07-07 | 南通硬派锂电池有限公司 | Method for inhibiting capacity attenuation of lithium manganate lithium ion battery |
| CN114361446A (en) * | 2021-12-29 | 2022-04-15 | 常州锂源新能源科技有限公司 | Method for testing low-temperature performance of lithium iron phosphate cathode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008027912A (en) * | 2006-07-14 | 2008-02-07 | Kumho Petrochem Co Ltd | Anode active material for lithium secondary cell mixed with carbon nanofiber |
| CN101809805A (en) * | 2008-06-12 | 2010-08-18 | 松下电器产业株式会社 | Charging method and discharging method of lithium ion secondary battery |
| CN101859887A (en) * | 2010-06-22 | 2010-10-13 | 华中科技大学 | Transition metal phosphate-clad composite lithium ion battery anode material |
| CN101958426A (en) * | 2009-07-16 | 2011-01-26 | 索尼公司 | Secondary cell, negative pole, positive pole and electrolyte |
-
2012
- 2012-05-07 CN CN201210136841.6A patent/CN102637876B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008027912A (en) * | 2006-07-14 | 2008-02-07 | Kumho Petrochem Co Ltd | Anode active material for lithium secondary cell mixed with carbon nanofiber |
| CN101809805A (en) * | 2008-06-12 | 2010-08-18 | 松下电器产业株式会社 | Charging method and discharging method of lithium ion secondary battery |
| CN101958426A (en) * | 2009-07-16 | 2011-01-26 | 索尼公司 | Secondary cell, negative pole, positive pole and electrolyte |
| CN101859887A (en) * | 2010-06-22 | 2010-10-13 | 华中科技大学 | Transition metal phosphate-clad composite lithium ion battery anode material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104577203A (en) * | 2014-05-21 | 2015-04-29 | 深圳市格瑞普电池有限公司 | Preparation method of lithium ion battery |
| CN106058224A (en) * | 2016-08-19 | 2016-10-26 | 周新凤 | Composite lithium battery cathode material and preparation method thereof |
| CN111384458A (en) * | 2019-12-25 | 2020-07-07 | 南通硬派锂电池有限公司 | Method for inhibiting capacity attenuation of lithium manganate lithium ion battery |
| CN114361446A (en) * | 2021-12-29 | 2022-04-15 | 常州锂源新能源科技有限公司 | Method for testing low-temperature performance of lithium iron phosphate cathode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102637876B (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105390671B (en) | The manufacturing method and positive electrode active material for lithium ion battery layer of positive electrode active material for lithium ion battery layer | |
| KR101678798B1 (en) | Method for producing nonaqueous electrolyte secondary battery | |
| KR101488043B1 (en) | Method for activating high capacity lithium secondary battery | |
| CN101308926B (en) | Lithium ionic cell composite positive pole material coated by orthosilicate and its preparation method | |
| CN105161693A (en) | High-cycle lithium ion battery multi-element anode material NCM and preparation method thereof | |
| CN1960040A (en) | High-powered lithium ferric phosphate dynamic battery, and preparation technique | |
| EP4220759A1 (en) | Lithium metal negative electrode plate, electrochemical apparatus, and electronic device | |
| CN102361095A (en) | Lithium ion battery with high specific power and preparation method for same | |
| CN105742703A (en) | High-voltage functional electrolyte containing LiDFOB additive and preparation and application thereof | |
| KR20170025874A (en) | Lithium secondary battery and operating method thereof | |
| CN108137346A (en) | For the precursor of the lithium transition-metal oxide cathode material of chargeable storage | |
| CN105470473A (en) | Positive electrode active material and secondary battery | |
| KR20160074386A (en) | Lithium ion secondary battery | |
| CN104051720A (en) | Material, preparation of material and lithium ion positive active material containing material, positive electrode material, battery positive-electrode and battery | |
| CN111082128B (en) | High-power all-solid-state battery and preparation thereof | |
| JP2011192561A (en) | Manufacturing method for nonaqueous electrolyte secondary battery | |
| CN105633464A (en) | Trimethyl borate additive contained high-voltage functional electrolyte and preparation method and application therefor | |
| CN102637876B (en) | Lithium battery anode material and method for improving cycle performance of battery | |
| CN107644980A (en) | Pre- embedding lithium hard carbon material and its preparation method and application | |
| JP6466065B2 (en) | Positive electrode material, positive electrode, and lithium ion battery | |
| KR20170092264A (en) | All solid lithium secondary batteries including conducting polymer and manufacturing method for the same | |
| JP2018195419A (en) | Positive electrode material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery arranged by use thereof, and method for manufacturing positive electrode material for nonaqueous electrolyte secondary battery | |
| KR101909317B1 (en) | Cathode active material for lithium secondary battery and method of making the same | |
| KR101142533B1 (en) | Metal based Zn Negative Active Material and Lithium Secondary Battery Comprising thereof | |
| CN112216867B (en) | Electrolyte additive, lithium ion high-voltage electrolyte and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141231 Termination date: 20160507 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |