CN102800841B - Negative plate, lithium ion battery and preparation method thereof - Google Patents
Negative plate, lithium ion battery and preparation method thereof Download PDFInfo
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- CN102800841B CN102800841B CN201210280590.9A CN201210280590A CN102800841B CN 102800841 B CN102800841 B CN 102800841B CN 201210280590 A CN201210280590 A CN 201210280590A CN 102800841 B CN102800841 B CN 102800841B
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a negative plate, comprising a negative current collector and a negative electrode coating coated on the negative current collector, wherein the negative electrode coating comprises a negative active material, a conductive agent and a bonding agent, and the negative active material comprises carbon coated lithium titanate particles which have a spinel structure. According to the invention, the negative active material of the negative plate comprises carbon coated lithium titanate, there is no change of the crystal form of the spinel lithium titanate in the process of intercalation/deintercalation of lithium ions, the crystal lattice constant has small change, and the volume change is less than 1%; when the negative plate is applied in a lithium ion battery, compared with a traditional lithium ion battery which comprises a graphite material as a negative active material, the battery cycle performance is better. The invention further provides a lithium ion battery which utilizes the negative plate and a preparation method thereof.
Description
Technical field
The present invention relates to energy storage device field, relate in particular to a kind of negative plate, adopt lithium ion battery of this negative plate and preparation method thereof.
Background technology
The energy and environment are two subject matters of 21st century facing mankind.In China, along with the acceleration of industrialization and urbanization process, economy constantly increases the demand of oil, and China's oil supply is obviously not enough, externally interdependent improving constantly.Meanwhile, along with increasing oil and coal are exploited and burn, in atmosphere, carbon dioxide isothermal chamber gas will constantly increase, and China facing increasing carbon emission reduction pressure.Developing new forms of energy is State construction Energy-saving Societies, alleviates the strategic measure that traditional energy is relied on, and is the inevitable choice of economic transition under carbon emission reduction pressure.Along with the utilization of regenerative resource, day by day universal as wind energy, solar energy and fuel cell etc., and peak load regulation network, raising electric network reliability and improve the active demand of the quality of power supply, it is more and more important that electric energy storing system seems.Large capacity energy-storage system also can be widely used in residential quarter, hospital, large enterprise etc. as emergency power supply and be applied to electric automobile as electrokinetic cell.
Lithium ion battery has high-energy-density because of it, and operating voltage is high, and power output is large, have extended cycle life, self-discharge rate is low, memory-less effect, the advantage such as environmentally friendly, be widely used in portable consumer electronics terminal field, also start at present to expand to energy field of traffic, as power vehicle, uninterrupted power supply, stand-by power supply, power station energy storage etc., this has higher requirement to aspects such as the energy density of lithium ion battery, cycle life, fail safes.
Traditional commercial lithium ion battery negative material is graphite material mostly, yet because the change in volume in graphite electrode charge and discharge process is larger, causes battery capacity to decline, and causes cycle performance variation.
Summary of the invention
Based on this, be necessary to provide a kind of cycle performance of battery good negative plate, adopt lithium ion battery of this negative plate and preparation method thereof.
A negative plate, comprises negative current collector and is coated in the negative pole coating on described negative current collector; Described negative pole coating comprises 80% ~ 94% negative active core-shell material, 3% ~ 10% conductive agent and 3% ~ 10% bonding agent according to mass percent;
Described negative active core-shell material is that lithium titanate particle and the described lithium titanate particle of coated with carbon has spinel structure.
In one embodiment, the particle diameter of the lithium titanate particle of described coated with carbon is 0.1 μ m ~ 10 μ m, and the specific area of the lithium titanate particle of described coated with carbon is 1m
2/ g ~ 20m
2/ g.
In one embodiment, described negative current collector is corrosive aluminum foil;
The thickness of described corrosive aluminum foil is 10 μ m ~ 30 μ m, and surperficial pore-creating rate is 20% ~ 80%, and the aperture of pore-creating is 0.1 μ m ~ 1 μ m.
A lithium ion battery, comprises shell, positive plate, negative plate, barrier film and electrolyte between described positive plate and described negative plate;
Described positive plate comprises plus plate current-collecting body and is coated in the anodal coating on described plus plate current-collecting body;
Described negative plate is negative plate as above.
In one embodiment, the ratio of the capacity per unit area of described positive plate and the capacity per unit area of negative plate is 1.02～1.2.
In one embodiment, described anodal coating comprises 80% ~ 96% positive electrode active materials, 2%～10% described conductive agent and 2%～10% described bonding agent according to mass percent;
Described positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one, or described positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one and LiCoO
2mixture, x+y+z=1 wherein, 0<x<1,0<y<1,0≤z<1, r+s+t=1,0<r<1,0<s<1,0<t<1, M is Al, Mg, Fe, Cr, Sn, Sr or Mn.
In one embodiment, described barrier film is polypropylene screen, polypropylene, polyethylene/polypropylene composite film, nylon cloth, glass fibre, polyvinyl alcohol film or asbestos paper;
The solute of described electrolyte is LiPF
6, LiBF
4, LiClO
4and LiAsF
6in at least one, solvent is at least one in vinyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, sub-vinyl carbonate and fluoro carbonic ester.
A preparation method for lithium ion battery, comprises the steps:
According to mass percent, 80% ~ 90% negative active core-shell material, 5% ~ 10% conductive agent, 5% ~ 10% binding agent are joined in solvent, after mixing, obtain cathode size, described cathode size is coated in to the dry rear negative pole coating that forms on negative current collector, obtains negative plate; Wherein, described negative active core-shell material is coated with carbon lithium titanate particle and described lithium titanate particle have spinel structure;
Anode sizing agent is provided, and described anode sizing agent is coated in to the dry rear anodal coating that forms on plus plate current-collecting body, obtain positive plate;
Positive plate, negative plate are reeled together with barrier film or lamination becomes battery core, pack into and in shell, inject electrolyte sealing, the lithium ion battery that obtains not changing into;
The described lithium ion battery not changing into is changed into, obtain described lithium ion battery.
In one embodiment, described solvent is 1-METHYLPYRROLIDONE, dimethylformamide or dimethylacetylamide.
In one embodiment, what the described lithium ion battery not changing into was changed into is operating as: by the described lithium ion cell charging not changing into high voltage, making negative electricity potential drop be low to moderate with respect to lithium current potential is below 0.6V, thereby forms the middle phase film of solid electrolyte in negative terminal surface.
The negative active core-shell material of this negative plate adopts the lithium titanate of coated with carbon, spinel lithium titanate embeds-deviates from crystal formation in process at lithium ion and do not change, lattice constant changes very little, change in volume is less than 1%, simultaneously due to coated with carbon, compare and improved conductivity with pure lithium titanate, improved the ability of absorption electrolyte.When this negative plate is applied to lithium ion battery, compare as the lithium ion battery of negative active core-shell material with traditional employing graphite material, cycle performance of battery is better.
Accompanying drawing explanation
Fig. 1 is preparation method's the flow chart of the lithium ion battery of an execution mode.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
The negative plate of one execution mode comprises negative current collector and is coated in the negative pole coating on negative current collector.
Negative pole coating comprises 80% ~ 94% negative active core-shell material, 3% ~ 10% conductive agent and 3% ~ 10% bonding agent according to mass percent.
Conductive agent is at least one in super conductive black, electrically conductive graphite and electrical-conductive nanometer carbon pipe.
Binding agent is at least one in polytetrafluoroethylene, Kynoar and polymer resin.
Negative active core-shell material is the lithium titanate particle of coated with carbon, and lithium titanate particle has spinel structure.
The lithium titanate particle of this coated with carbon can prepare, and also can directly buy the product of business.
The particle diameter of the lithium titanate particle of coated with carbon can be 0.1 μ m ~ 10 μ m, and the specific area of the lithium titanate particle of coated with carbon can be 1m
2/ g ~ 20m
2/ g.
When the particle diameter of the lithium titanate particle of coated with carbon is less than 0.1 μ m, materials processing performance is bad, and material easily absorbs water.When the particle diameter of the lithium titanate particle of coated with carbon is greater than 10 μ m, high-rate battery discharge degradation.
Preferably, the particle diameter of the lithium titanate particle of coated with carbon is 0.2 μ m ~ 5 μ m.
In present embodiment, negative current collector is corrosive aluminum foil.
The negative active core-shell material of this negative plate adopts the lithium titanate of coated with carbon, spinel lithium titanate embeds-deviates from crystal formation in process at lithium ion and do not change, lattice constant changes very little, change in volume is less than 1%, simultaneously due to coated with carbon, compare and improved conductivity with pure lithium titanate, improved the ability of absorption electrolyte.When this negative plate is applied to lithium ion battery, compare as the lithium ion battery of negative active core-shell material with traditional employing graphite material, cycle performance of battery is better.
For pure lithium titanate particle surface smoother, bad adhesion between lithium titanate anode material and optical aluminum foil, lithium titanate material conductivity is low, lithium titanate battery internal resistance is large, the problems such as performance that are unfavorable for battery capacity and high rate performance, the negative active core-shell material of this negative plate adopts the lithium titanate particle of coated with carbon, collector adopts through the corrosive aluminum foil of corrosion treatment and makes lithium titanate anode sheet, thereby improved adhesive property between lithium titanate anode material and aluminium foil, reduce the internal resistance of cell, improved high-rate battery discharge performance.
The lithium ion battery of one execution mode, comprises shell, positive plate, negative plate, the barrier film between positive plate and negative plate and electrolyte.
After positive plate, negative plate and membrane winding or lamination, form battery core, pack in shell, electrolyte injects shell, forms lithium ion battery after sealing.
Barrier film can be polypropylene screen, polypropylene, polyethylene/polypropylene composite film, nylon cloth, glass fibre, polyvinyl alcohol film or asbestos paper.
The solute of electrolyte can be LiPF
6, LiBF
4, LiClO
4and LiAsF
6in at least one, solvent can be at least one in vinyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, sub-vinyl carbonate and fluoro carbonic ester.
Negative plate comprises negative current collector and is coated in the negative pole coating on negative current collector.
Negative pole coating comprises 80% ~ 94% negative active core-shell material, 3% ~ 10% conductive agent and 3% ~ 10% bonding agent according to mass percent.
Conductive agent is at least one in super conductive black, electrically conductive graphite and electrical-conductive nanometer carbon pipe.
Binding agent is at least one in polytetrafluoroethylene, Kynoar and polymer resin.
Negative active core-shell material is the lithium titanate particle of coated with carbon, and lithium titanate particle has spinel structure.
The lithium titanate particle of this coated with carbon can prepare, and also can directly buy the product of business.
The particle diameter of the lithium titanate particle of coated with carbon can be 0.1 μ m ~ 10 μ m, and the specific area of the lithium titanate particle of coated with carbon can be 1m
2/ g ~ 20m
2/ g.
Preferably, the particle diameter of the lithium titanate particle of coated with carbon is 0.2 μ m ~ 5 μ m.
In present embodiment, negative current collector is corrosive aluminum foil.
The thickness of above-mentioned corrosive aluminum foil can be 10 μ m ~ 30 μ m, and surperficial pore-creating rate can be 20% ~ 80%, and the aperture of pore-creating can be 0.1 μ m ~ 1 μ m.
Positive plate comprises plus plate current-collecting body and is coated in the anodal coating on plus plate current-collecting body.
Plus plate current-collecting body can be aluminium foil.
Anodal coating comprises 80% ~ 96% positive electrode active materials, 2% ~ 10% above-mentioned conductive agent and 2% ~ 10% above-mentioned bonding agent according to mass percent.
Positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one, or positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one and LiCoO
2mixture, x+y+z=1 wherein, 0<x<1,0<y<1,0≤z<1, r+s+t=1,0<r<1,0<s<1,0<t<1, M is Al, Mg, Fe, Cr, Sn, Sr or Mn.
The ratio of the capacity per unit area of positive plate and the capacity per unit area of negative plate is 1.02 ~ 1.2.
The ratio of the capacity per unit area of positive plate and the capacity per unit area of negative plate is greater than 1, makes positive electrode active materials excessive, thereby has guaranteed the safety of battery in overcharging formation process, makes battery have longer cycle life simultaneously.
The negative active core-shell material of this lithium ion battery adopts the lithium titanate of coated with carbon, spinel lithium titanate embeds-deviates from crystal formation in process at lithium ion and do not change, lattice constant changes very little, change in volume is less than 1%, simultaneously due to coated with carbon, compare and improved conductivity with pure lithium titanate, improved the ability of absorption electrolyte.This lithium ion battery is compared as the lithium ion battery of negative active core-shell material with traditional employing graphite material, and cycle performance of battery is better.
For pure lithium titanate particle surface smoother, bad adhesion between lithium titanate anode material and optical aluminum foil, lithium titanate material conductivity is low, lithium titanate battery internal resistance is large, the problems such as performance that are unfavorable for battery capacity and high rate performance, the negative active core-shell material of this lithium ion battery adopts the lithium titanate particle of coated with carbon, collector adopts through the corrosive aluminum foil of corrosion treatment and makes lithium titanate anode sheet, thereby improved adhesive property between lithium titanate anode material and aluminium foil, reduce the internal resistance of cell, improved high-rate battery discharge performance.
The preparation method of above-mentioned lithium ion battery as shown in Figure 1, comprises the steps:
S10, according to mass percent, the lithium titanate particle of 80% ~ 94% coated with carbon, 3% ~ 10% conductive agent and 3% ~ 10% binding agent are joined in solvent, after mixing, obtain cathode size, described cathode size is coated in to the dry rear negative pole coating that forms on negative current collector, obtains negative plate.
In cathode size, solute solid content is 30% ~ 70%.
Cathode size is coated in to negative current collector two sides, through baking, roll-in, section, makes negative plate.
Solvent can be 1-METHYLPYRROLIDONE (NMP), dimethylformamide or dimethylacetylamide.
Conductive agent is at least one in super conductive black, electrically conductive graphite and electrical-conductive nanometer carbon pipe.
Binding agent is at least one in polytetrafluoroethylene, Kynoar and polymer resin.
Negative active core-shell material is the lithium titanate particle of coated with carbon, and lithium titanate particle has spinel structure.
The lithium titanate particle of this coated with carbon can prepare, and also can directly buy the product of business.
The particle diameter of the lithium titanate particle of coated with carbon can be 0.1 μ m ~ 10 μ m, and the specific area of the lithium titanate particle of coated with carbon can be 1m
2/ g ~ 20m
2/ g.
Preferably, the particle diameter of the lithium titanate particle of coated with carbon is 0.2 μ m ~ 5 μ m.
In present embodiment, negative current collector is corrosive aluminum foil.
The thickness of above-mentioned corrosive aluminum foil can be 10 μ m ~ 30 μ m, and surperficial pore-creating rate can be 20% ~ 80%, and the aperture of pore-creating can be 0.1 μ m ~ 1 μ m.
S20, provide anode sizing agent, and described anode sizing agent is coated in after dry on plus plate current-collecting body and forms anodal coating, obtain positive plate.
Anode sizing agent can make as follows: according to mass percent, 80% ~ 96% positive electrode active materials, 2% ~ 10% above-mentioned conductive agent, 2% ~ 10% above-mentioned binding agent are joined in above-mentioned solvent, after mixing, obtain anode sizing agent.
Anode sizing agent is coated in to plus plate current-collecting body two sides, through baking, roll-in, section, makes positive plate.
Solvent can be 1-METHYLPYRROLIDONE, dimethylformamide or dimethylacetylamide.
Conductive agent is at least one in super conductive black, electrically conductive graphite and electrical-conductive nanometer carbon pipe.
Binding agent is at least one in polytetrafluoroethylene, Kynoar and polymer resin.
Positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one, or positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one and LiCoO
2mixture, x+y+z=1 wherein, 0<x<1,0<y<1,0≤z<1, r+s+t=1,0<r<1,0<s<1,0<t<1, M is Al, Mg, Fe, Cr, Sn, Sr or Mn.
Plus plate current-collecting body can be aluminium foil.
The order that is understandable that S10 and S20 can be changed.
The positive plate that S30, the negative plate that S10 is obtained, S20 obtain is reeled together with barrier film or lamination becomes battery core, packs injection electrolyte sealing in shell into, the lithium ion battery that obtains not changing into.
Barrier film can be polypropylene screen, film, polypropylene, polyethylene/polypropylene composite film, nylon cloth, glass fibre, polyvinyl alcohol film or asbestos paper.
The solute of electrolyte is LiPF
6, LiBF
4, LiClO
4and LiAsF
6in at least one, solvent is at least one in vinyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, sub-vinyl carbonate and fluoro carbonic ester.
Shell is used for sealing battery core and electrolyte, and concrete shape is unrestricted.
S40, the lithium ion battery not changing into that S30 is obtained change into, and obtain lithium ion battery.
After the lithium ion battery not changing into that S30 is obtained changes into, also comprise cell degradation, degasification, the processing such as sealing, partial volume, detection, thus obtain finished product lithium ion battery.
The concrete operations that the lithium ion battery not changing into is changed into are: by the lithium ion cell charging not changing into high voltage, making negative electricity potential drop be low to moderate with respect to lithium current potential is below 0.6V, thereby forms the middle phase film (SEI) of solid electrolyte in negative terminal surface.
The lithium ion cell charging not changing into is selected different differently to high-tension concrete voltage because of positive electrode, and technical essential is that to make negative electricity potential drop be low to moderate with respect to lithium current potential be below 0.6V.
For the lithium ion battery that adopts pure lithium titanate as cell negative electrode material, in use and storage process, there is flatulence, the embedding lithium current potential high (being about 1.5V(vs.Li/Li+) of lithium titanate), can not form the problems such as SEI film under normal circumstances, formation process charges to high voltage by battery, making negative electricity potential drop be low to moderate with respect to lithium current potential is below 0.6V, thereby in negative terminal surface, form the middle phase film (SEI) of solid electrolyte, overcome the flatulence problem of lithium titanate battery.
Be below specific embodiment, the lithium titanate of the coated with carbon adopting in specific embodiment is all purchased from Shenzhen Bei Terui company, and material model is LTO-1, and particle size range is 0.2 μ m ~ 5 μ m, and specific area is 1m
2/ g ~ 16m
2/ g.
Embodiment 1
By mass percentage the lithium titanate of 90% coated with carbon, 3% SP, 2% KS-6 and 5% PVDF are added in stirred tank, vacuumize and stir, add appropriate NMP to continue to stir, obtain cathode size, cathode size is coated on to the thick porous corrosive aluminum foil two sides through corrosion treatment of 20 μ m, and pole piece coat side density is 250g/m
2, through baking, roll-in, section, make negative plate.
In mass ratio by 94% LiMn
2o
4, 1.5% SP, 1.5% KS-6 and 3% PVDF are dissolved in NMP stirring and make anode sizing agent, and anode sizing agent is coated on to optical aluminum foil two sides, and surface density is 400g/m
2, through baking, roll-in, section, make positive plate.
By controlling coat side density, the ratio of the capacity per unit area of positive plate and the capacity per unit area of negative plate is greater than 1, and the ratio of finally controlling the capacity per unit area of positive plate and the capacity per unit area of negative plate is 1.02 ~ 1.2.
The positive plate of making, negative plate are wound into battery core together with polypropylene diaphragm, and dress shell, injects organic electrolyte sealing, and electrolyte is the EC/EMC/DEC solution (EC/EMC/DEC volume ratio is 1:1:1) of 1M LiPF6.
Battery standing changes into after a period of time, and formation process charges to 3.7V by battery, thereby forms the middle phase film (SEI) of solid electrolyte in negative terminal surface.
Change into and rear battery is carried out to aging, degasification, sealing, partial volume, Check processing, make lithium ion battery.
Embodiment 2
Difference from Example 1, positive electrode active materials is LiMn
2o
4with LiCoO
2mixture (part by weight is 8:2), is coated on optical aluminum foil two sides by anodal coating, and surface density is 370g/m
2.
Embodiment 3
Difference from Example 1, positive electrode active materials is LiNi
0.5mn
0.3co
0.2o
2, anode sizing agent is coated on to optical aluminum foil two sides, in the solute of anode sizing agent, comprise by mass percentage 95% LiNi
0.5mn
0.3co
0.2o
2, 2% SP, 1% KS-6 and 2% PVDF, surface density is 250g/m
2, formation process charges to 3.5V by battery.
Embodiment 4
Difference from Example 1, comprises by mass percentage in the solute of cathode size and lithium titanate, 5% SP, 5% KS-6 and 10% the PVDF of 80% coated with carbon in the solute of anode sizing agent, comprises by mass percentage 80% LiMn
2o
4, 5% SP, 5% KS-6 and 10% PVDF, formation process charges to 3.5V by battery.
Comparative example 1
By mass percentage the modified lithium titanate of 90% carbon coated, 3% SP, 2% KS-6,5% PVDF are added in stirred tank, vacuumize and stir, add appropriate NMP to continue to stir, obtain cathode size, cathode size is coated on to the thick optical aluminum foil of 16 μ m two sides, and surface density is 250g/m
2, through baking, roll-in, section, make negative plate.
In mass ratio by 94% LiMn
2o
4, 1.5% SP, 1.5% KS-6 and 3% PVDF are dissolved in NMP stirring and make anode sizing agent, and anode sizing agent is coated on to optical aluminum foil two sides, and surface density is 400g/m
2, through baking, roll-in, section, make positive plate.
The positive plate of making, negative plate are wound into battery core together with polypropylene diaphragm, and dress shell, injects organic electrolyte sealing, and electrolyte is the EC/EMC/DEC solution (EC EMC DEC volume ratio is 1:1:1) of 1M LiPF6.
Battery standing changes into after a period of time, and formation process charges to 3.7V by battery, thereby forms the middle phase film (SEI) of solid electrolyte in negative terminal surface.
Change into rear battery is carried out aging, degasification, sealing, partial volume, Check processing, make long-life titanium acid lithium battery.
Example example 1 and comparative example 1 battery performance are compared as follows.
Comparative example 2
With comparative example 1 difference, negative active core-shell material is the pure lithium titanate of carbon coated not, and cathode size is coated on the thick porous corrosive aluminum foil two sides through corrosion treatment of 20 μ m.
Example example 1 and comparative example 2 battery performances are compared as follows.
Comparative example 3
With comparative example 1 difference, cathode size is coated on the thick porous corrosive aluminum foil two sides through corrosion treatment of 20 μ m, and formation process charges to 2.8V by battery, make negative pole current potential with respect to lithium current potential higher than 0.6V.
Embodiment 1 and comparative example 3 battery performances are compared as follows.
The above results shows, pure lithium titanate is as bad adhesion between lithium ion battery anode active material and optical aluminum foil, and lithium titanate material conductivity is low, and lithium titanate battery internal resistance is large, is unfavorable for the problems such as performance of battery capacity and high rate performance.Adopt the lithium titanate of coated with carbon as negative active core-shell material, adopt the corrosive aluminum foil of process corrosion treatment as negative current collector, the negative plate of making, has improved adhesive property between lithium titanate anode material and aluminium foil, reduce the internal resistance of cell, improved high-rate battery discharge performance.Formation process charges to high voltage by battery, and making negative electricity potential drop be low to moderate with respect to lithium current potential is below 0.6V, thereby forms the middle phase film (SEI) of solid electrolyte in negative terminal surface, has overcome the flatulence problem of lithium titanate battery.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (5)
1. a lithium ion battery, comprises shell, positive plate, negative plate, barrier film and electrolyte between described positive plate and described negative plate; It is characterized in that,
Described positive plate comprises plus plate current-collecting body and is coated in the anodal coating on described plus plate current-collecting body;
Described negative plate comprises negative current collector and is coated in the negative pole coating on described negative current collector; Described negative pole coating comprises 80%～94% negative active core-shell material, 3%～10% conductive agent and 3%～10% bonding agent according to mass percent;
Described negative active core-shell material is that lithium titanate particle and the described lithium titanate particle of coated with carbon has spinel structure;
The particle diameter of the lithium titanate particle of described coated with carbon is 0.1 μ m～10 μ m, and the specific area of the lithium titanate particle of described coated with carbon is 1m
2/ g～20m
2/ g;
Described negative current collector is corrosive aluminum foil;
The thickness of described corrosive aluminum foil is 10 μ m～30 μ m, and surperficial pore-creating rate is 20%～80%, and the aperture of pore-creating is 0.1 μ m～1 μ m;
The ratio of the capacity per unit area of described positive plate and the capacity per unit area of negative plate is 1.02～1.2.
2. lithium ion battery according to claim 1, is characterized in that, described anodal coating comprises 80%～96% positive electrode active materials, 2%～10% described conductive agent and 2%～10% described bonding agent according to mass percent;
Described positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one, or described positive electrode active materials is LiMn
2o
4, LiNi
xco
ym
zo
2, LiNi
rmn
sco
to
2and LiFePO
4in at least one and LiCoO
2mixture, x+y+z=1 wherein, 0<x<1,0<y<1,0≤z<1, r+s+t=1,0<r<1,0<s<1,0<t<1, M is Al, Mg, Fe, Cr, Sn, Sr or Mn.
3. lithium ion battery according to claim 1, is characterized in that, described barrier film is polypropylene screen, polypropylene, polyethylene/polypropylene composite film, nylon cloth, glass fibre, polyvinyl alcohol film or asbestos paper;
The solute of described electrolyte is LiPF
6, LiBF
4, LiClO
4and LiAsF
6in at least one, solvent is at least one in vinyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, sub-vinyl carbonate and fluoro carbonic ester.
4. a preparation method for lithium ion battery, is characterized in that, comprises the steps:
According to mass percent, 80%～90% negative active core-shell material, 5%～10% conductive agent, 5%～10% binding agent are joined in solvent, after mixing, obtain cathode size, described cathode size is coated in to the dry rear negative pole coating that forms on negative current collector, obtains negative plate; Wherein, described negative active core-shell material is coated with carbon lithium titanate particle and described lithium titanate particle have spinel structure;
Anode sizing agent is provided, and described anode sizing agent is coated in to the dry rear anodal coating that forms on plus plate current-collecting body, obtain positive plate;
Positive plate, negative plate are reeled together with barrier film or lamination becomes battery core, pack into and in shell, inject electrolyte sealing, the lithium ion battery that obtains not changing into;
The described lithium ion battery not changing into is changed into, obtain described lithium ion battery;
The particle diameter of the lithium titanate particle of described coated with carbon is 0.1 μ m～10 μ m, and the specific area of the lithium titanate particle of described coated with carbon is 1m
2/ g～20m
2/ g;
Described negative current collector is corrosive aluminum foil;
The thickness of described corrosive aluminum foil is 10 μ m～30 μ m, and surperficial pore-creating rate is 20%～80%, and the aperture of pore-creating is 0.1 μ m～1 μ m;
The ratio of the capacity per unit area of described positive plate and the capacity per unit area of negative plate is 1.02～1.2;
What the described lithium ion battery not changing into was changed into is operating as: by the described lithium ion cell charging not changing into, to high voltage, making negative electricity potential drop be low to moderate with respect to lithium current potential is below 0.6V, thereby forms the middle phase film of solid electrolyte in negative terminal surface.
5. the preparation method of lithium ion battery according to claim 4, is characterized in that, described solvent is 1-METHYLPYRROLIDONE, dimethylformamide or dimethylacetylamide.
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| CN103022555B (en) * | 2012-12-30 | 2014-12-03 | 无锡富洪科技有限公司 | Lithium ion battery and preparation method thereof |
| CN104332656A (en) * | 2013-07-22 | 2015-02-04 | 浙江万向亿能动力电池有限公司 | Method for solving expanding of lithium ion battery using lithium titanate as negative electrode |
| CN103746139B (en) * | 2013-12-10 | 2016-02-10 | 宁波维科电池股份有限公司 | The lithium-ion-power cell that security performance is good |
| WO2017049471A1 (en) * | 2015-09-23 | 2017-03-30 | Basf Corporation | Electrolyte for lto type lithium ion batteries |
| CN105226325B (en) * | 2015-10-22 | 2017-07-28 | 郑州宇通客车股份有限公司 | A kind of lithium titanate battery electrolyte and lithium titanate battery |
| CN105932226B (en) * | 2016-05-19 | 2018-11-13 | 宁德时代新能源科技股份有限公司 | Drying method of battery pole piece |
| CN106848286B (en) * | 2017-02-13 | 2019-06-11 | 欣旺达电子股份有限公司 | The preparation method of lithium titanate material, porous lithium titanate material and lithium ion battery |
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| CN109638212A (en) * | 2018-11-20 | 2019-04-16 | 东莞锂威能源科技有限公司 | A kind of high magnification fast charge lithium ion battery |
| CN111326717B (en) * | 2018-12-13 | 2021-11-16 | 深圳先进技术研究院 | Aluminum negative electrode material, preparation method and secondary battery |
| CN110729529A (en) * | 2019-10-21 | 2020-01-24 | 中国科学院电工研究所 | Energy storage battery cell with composite electrode structure and method for pre-embedding lithium in battery cell |
| CN113346125A (en) * | 2021-05-31 | 2021-09-03 | 廖福宁 | Lithium ion battery |
| CN114583289A (en) * | 2022-03-31 | 2022-06-03 | 珠海冠宇电池股份有限公司 | Lithium ion battery |
| CN115513537A (en) * | 2022-10-08 | 2022-12-23 | 湖北钛时代新能源有限公司 | Preparation method of lithium iron phosphate battery for energy storage |
| WO2024087817A1 (en) * | 2022-10-24 | 2024-05-02 | 珠海冠宇电池股份有限公司 | Negative electrode sheet and lithium-ion battery |
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| CN101582522A (en) * | 2009-06-23 | 2009-11-18 | 珠海市鹏辉电池有限公司 | High rate charge-discharge power lithium battery |
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