CN104362346A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN104362346A CN104362346A CN201410542073.3A CN201410542073A CN104362346A CN 104362346 A CN104362346 A CN 104362346A CN 201410542073 A CN201410542073 A CN 201410542073A CN 104362346 A CN104362346 A CN 104362346A
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- active material
- lithium ion
- carbon
- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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 belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery. The lithium ion battery comprises a positive plate, a negative plate, an isolating membrane spaced between the positive plate and the negative plate and electrolyte, wherein the positive plate comprises a positive current collector and a positive active material layer arranged on the surface of the positive current collector; the positive active material layer comprises components in percentage by mass as follows: 98.1%-99.8% of positive active materials, 0.1%-1% of a positive conductive agent and 0.1%-1% of a positive adhesive; and a negative conductive agent comprises at least one of carbon fiber, carbon nano tubes, carbon nanorods and graphene or a mixture of carbon black with at least one of carbon fiber, carbon nano tubes, carbon nanorods and graphene. Compared with the prior art, the energy density of the battery and the high-power charge and discharge characteristics of the battery are improved under the premise that a diaphragm isn't separated.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of lithium ion battery with high-energy-density and high rate charge-discharge characteristic.
Background technology
Lithium ion battery is as a kind of function element of clean environment firendly, obtain in increasing field at present and applied more and more widely, such as, in consumer electronics sector, electric automobiles, energy-storage system field and balance car field etc. emerging recently.
Wherein, the consumption electronic product that people commonly use, as mobile phone and notebook computer etc. use power increasing, therefore they require also increasing to the flying power of lithium ion battery.The flying power of lithium ion battery is mainly reflected in its energy density and charging rate two aspects.At present, the lifting of the energy density of lithium ion battery is increasingly difficult, and expands the charging rate of lithium ion battery, and the charging interval shortening unit quantity of electricity is the effective way strengthening flying power.
The charging rate improving lithium ion battery can from improving charging method, improving battery chemistries system and improve the aspects such as battery structure and carry out.So far have many patents or application discloses and change charging method to promote the technical scheme of charging rate, but about the battery chemistries system that can fill soon, the report especially relating to the battery chemistries system that can fill soon of high-energy-density is less.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and under a kind of prerequisite ensureing diaphragm not demoulding being provided, both can improving the energy density of battery, the lithium ion battery of its high rate charge-discharge characteristic can be improved again.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of lithium ion battery, comprise positive plate, negative plate, be arranged at intervals at barrier film between described positive plate and described negative plate, and electrolyte, described positive plate comprises plus plate current-collecting body and is arranged at the positive electrode active material layer of described anode collection surface, by mass percentage, described positive electrode active material layer comprises following component:
Positive active material 98.1% ~ 99.8%;
Positive conductive agent 0.1% ~ 1%;
Positive pole bonding agent 0.1% ~ 1%;
Described positive conductive agent is at least one in carbon fiber, carbon nano-tube, carbon nano rod and Graphene, or is the mixture of at least one in carbon fiber, carbon nano-tube, carbon nano rod, phosphorus shape graphite, Graphene and carbon black.In these positive conductive agent, carbon fiber, carbon nano-tube, carbon nano rod are one-dimensional material, and phosphorus shape graphite and Graphene are two-dimensional material, and carbon black is zero dimension material.
Relative to prior art, the present invention has following beneficial effect:
First, use one dimension/two-dimentional electric conducting material or one dimension/two-dimentional electric conducting material mixed as conductive agent with zero dimension material carbon black, can to connect better positive active material particle, conductive effect is better, thus the content of conductive agent can be reduced, simultaneously, these conductive agents also play the effect of similar binding agent, the diameter of the size specific activity material grains of one dimension/two-dimentional conductive agent is much larger, certain constraint effect can be played, two dimension conductive agent then can directly wrap up multiple active particle, be similar to binding agent thus suitably can reduce the content of bonding agent, improve positive active material content, and then lifting energy density.
Secondly, because bonding agent is non-conductive polymer substance, it is coated on positive active material surface can play the effect connecting adjacent particle, but so just hinder the electrical conductivity of conductive agent, larger to the kinetic effect of electrode, therefore, the content reducing bonding agent can promote high rate performance largely, specifically, the content reducing bonding agent can improve the removal lithium embedded dynamic performance of positive electrode electronic conductance and positive pole, reduce polarization, increase the constant current time of charging process, thus promote charging rate.But the content of bonding agent again can not be too little, otherwise the easy demoulding of positive pole diaphragm.Facts have proved, in the present invention, the content of positive pole bonding agent can ensure that within 0.1% ~ 1% positive pole diaphragm demoulding does not occur.
Again, the bonding agent being coated on positive active particles surface belongs to ion conductor, but non-conductive son, conductive agent then belongs to electronic conductor, but not diversion is sub.One dimension/two-dimentional electric conducting material or one dimension/two-dimentional electric conducting material is mixed with zero dimension material carbon black add as conductive agent after, conductive network is become with bonding agent interconnects, it is also electronic conductor that this conductive network is not only ion conductor, significantly can increase the avtive spot of electro transfer, also provide lithium ion simultaneously and embed at electrode surface the conductive channel of deviating from.So greatly can promote the high rate performance of battery core.
Generally speaking, the present invention is by selecting reasonably formula and applicable conductive agent dexterously, under the prerequisite ensureing diaphragm not demoulding, both can improve the energy density of battery, improved again high rate charge-discharge characteristic (i.e. large circulation performance) and the charging rate of battery.
One as lithium ion battery of the present invention is improved, and described negative plate comprises negative current collector and is arranged at the negative electrode active material layer of described negative pole currect collecting surface, and by mass percentage, described negative electrode active material layer comprises following component:
Negative electrode active material 80% ~ 97%;
Cathode conductive agent 1% ~ 18%;
Negative pole bonding agent 1% ~ 18%;
Negative pole stabilizer 1% ~ 18%.
One as lithium ion battery of the present invention is improved, and described positive active material is at least one in nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, cobalt acid lithium, lithium nickelate and LiFePO4.
One as lithium ion battery of the present invention is improved, and the percentage by weight that described positive active material accounts for active material doped with quality is the metallic element of 0.1%-1%, and described metallic element is selected from least one in Mg, Zr, Ti, Zn, V and Cr.In positive active material, doped metallic elements can improve its structural stability.
One as lithium ion battery of the present invention is improved, and the Surface coating of described positive active material has oxide cladding layers or carbon-coating, and described oxide cladding layers is selected from Al
2o
3, ZrO
2, Y
2o
3, MgO and TiO
2in at least one, the ratio of the quality of described oxide cladding layers or described carbon-coating and the quality of described positive active material is (0.1-2): 100.Can improve its structural stability at positive active material oxide coated on surface layer, carbon-coating is then mainly for LiFePO4, and carbon-coating can improve its electrical conductance.
One as lithium ion battery of the present invention is improved, and described negative electrode active material is at least one in Delanium, native graphite, carbonaceous mesophase spherules, soft carbon, hard carbon, silicon, silicon dioxide and ashbury metal.
One as lithium ion battery of the present invention is improved, and described negative pole bonding agent and described positive pole bonding agent are at least one in Kynoar, butadiene-styrene rubber, sodium alginate, polyvinyl alcohol and polytetrafluoroethylene.
One as lithium ion battery of the present invention is improved, and described negative pole stabilizer is at least one in sodium carboxymethylcellulose, hydroxypropyl methylcellulose sodium and sodium cellulose glycolate; Described cathode conductive agent is carbon black, or is at least one in carbon fiber, carbon nano-tube, carbon nano rod and Graphene, or is the mixture of at least one in carbon fiber, carbon nano-tube, carbon nano rod, phosphorus shape graphite, Graphene and carbon black.
One as lithium ion battery of the present invention is improved, and described electrolyte comprises organic solvent, additive and lithium salts, and described additive comprises at least one in 12-crown ether-4, three (pentafluorophenyl group) borine and pentafluorophenyl group boron oxalate.
12-crown ether-4 is a kind of conductive additives, 4 oxygen atoms in its molecule and Li+ coordination, forms clad type chelate, effectively solvent molecule, lithium salts anion can be separated with lithium ion, improve lithium salts solubility, increases the conductivity of electrolyte.In addition, 12-crown ether-4 add the common embedding Sum decomposition that can reduce solution in charging process, the chemical property of negative material in the organic electrolytes such as carbonic ester is also improved.In addition, 12-crown ether-4 has multiple oxygen-containing functional group, belongs to nucleophilic functional group, in charging process, 12-crown ether-4 to cover on positive electrode particle surface, when lithium ion is deviate from, because nucleophilic effect 12-crown ether-4 can carry out coordination with lithium ion, play the effect of solvation, lithium ion is made to depart from crystalline body, increase the diffusion velocity that positive pole takes off lithium ion after lithium, decrease concentration polarization, thus improve the kinetics performance of positive pole.
During using PFPBO as lithium ion battery additive, the oxide (Li of LiF, lithium
2o, Li
2o
2) solubility in PC/DMC (1:1, v/v) significantly increases, electrolyte conductance is high, Li
+transference number of ions is large, can accelerate between lithium ion porous electrode diffusion, reduce lithium ion migration resistance in the electrolytic solution.
TPFPB can make LiF solubility reach 1.0M, it significantly can improve life-span of battery, conductive capability and thermal stability, this is because, TPFPB can promote LiF stripping from SEI film, reduce the resistance of SEI film, and it can also improve the transference number of ions of Li+, improve the conductivity of electrolyte solution.By selecting the additive with high electrical conductivity, the electric conductivity of battery system can be improved, thus improve the large multiplying power charge characteristic of battery further.
One as lithium ion battery of the present invention is improved, and the concentration of described lithium salts is 1.0-1.3mol/L, and higher lithium salt can ensure that battery system has higher electric conductivity, thus improves the large multiplying power charge characteristic of battery further.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention and Advantageous Effects thereof are described in detail.
Fig. 1 is the 5C charging rate curve of embodiments of the invention 1 and comparative example 1.
Fig. 2 is the 10C/10C cyclic curve of embodiments of the invention 1 and comparative example 1.
Embodiment
Embodiment 1
A kind of lithium ion battery that the present embodiment provides, comprises positive plate, negative plate, is arranged at intervals at barrier film between positive plate and negative plate, and electrolyte;
Positive plate comprises plus plate current-collecting body and is arranged at the positive electrode active material layer of anode collection surface, and by mass percentage, positive electrode active material layer comprises following component:
Positive active material nickle cobalt lithium manganate 98.5%;
Positive conductive agent carbon black 0.3%;
Positive conductive agent carbon nano-tube 0.4%;
Positive pole bonding agent Kynoar 0.8%;
Plus plate current-collecting body to be thickness the be aluminium foil of 16 μm.
Negative plate comprises negative current collector and is arranged at the negative electrode active material layer of negative pole currect collecting surface, and by mass percentage, negative electrode active material layer comprises following component:
Negative electrode active material native graphite 90%;
Cathode conductive agent carbon black 5%;
Negative pole bonding agent butadiene-styrene rubber 2.5%;
Negative pole stabilizer sodium carboxymethylcellulose (CMC) 2.5%;
Negative current collector to be thickness the be Copper Foil of 12 μm.
Electrolyte comprises organic solvent, additive and lithium salts, organic solvent is the mixture of dimethyl carbonate, diethyl carbonate and ethylene carbonate, the volume ratio of three is 2:2:3, additive comprise the mass ratio accounting for electrolyte gross mass be 1% 12-crown ether-4 and the mass ratio that accounts for electrolyte gross mass be the FEC of 2%, lithium salts is LiFP
6, concentration is 1.2mol/L.
Barrier film to be thickness the be polyethylene of 16 μm.
The preparation method of the battery of the present embodiment is:
The preparation of positive plate: by the nickle cobalt lithium manganate of 98.5%, 0.3% carbon black, the carbon nano-tube of 0.4%, the PVDF of 0.8% add in 1-METHYLPYRROLIDONE and be mixed into slurry, be evenly coated on aluminium foil, make its surface density be 18mg/cm
2, drying, roll-in, cut after, obtain positive plate;
The preparation of negative plate: by the native graphite of 90%, the carbon black of 5%, the butadiene-styrene rubber of 2.5% and 2.5% CMC add in distilled water and be mixed into slurry, be then evenly coated on Copper Foil, make its surface density be 10mg/cm
2, drying, roll-in, cut after, obtain negative plate;
The preparation of battery core: positive plate, negative plate and barrier film are wound into battery core, wherein positive plate and negative plate are isolated film and separate, then on positive plate and negative plate, positive pole ear and negative lug is fixed respectively by ultrasonic bonding, finally battery core is placed in aluminum plastic film, baking, the moisture in removing battery core;
Fluid injection: inject a certain amount of above-mentioned electrolyte in the battery core after above-mentioned baking, seal and leave standstill, makes positive plate, negative plate and barrier film all fully infiltrate in the electrolytic solution;
Finally, above-mentioned battery core is changed into, aging through after a while, obtain powerful lithium ion battery.
Comparative example 1
As different from Example 1: the mass content of nickle cobalt lithium manganate is 90%, and conductive agent is carbon black, and the mass content of carbon black is 5%, the mass content of bonding agent is 5%, and not containing 12-crown ether-4 in electrolyte, the concentration of lithium salts is 1mol/L, all the other, with embodiment 1, repeat no more here;
Capacity and charge-discharge test are carried out to the battery that embodiment 1 and comparative example 1 provide, rate of charge is set to 5C and 10C, acquired results is in table 1, in addition, Fig. 1 also show 5C (multiplying power) the charging rate curve of embodiment 1 and comparative example 1, as can be seen from table 1 and Fig. 1: battery of the present invention has higher energy density lifting and charging rate lifting compared to the battery of comparative example 1.
Cycle life test is carried out to the battery that embodiment 1 and comparative example 1 provide, circulation is set to the acceleration circulation that 10C charging/10C discharges, acquired results is in table 1 and Fig. 2, as can be seen from table 1 and Fig. 2: battery of the present invention is in circulation after 1000 weeks, capacity still remains on more than 95%, the battery of comparative example 1 is then below 85%, and this shows that battery of the present invention has better high rate charge-discharge characteristic.
Embodiment 2
As different from Example 1: positive active material is nickel cobalt lithium aluminate, and its mass content is 98.8%, be also the Mg of 0.5% doped with mass percent and in nickel cobalt lithium aluminate; Positive conductive agent is carbon nano-tube, and its mass content is 0.5%; Positive pole bonding agent is sodium alginate, and its mass content is 0.7%; Additive comprise the mass ratio accounting for electrolyte gross mass be 1.5% three (pentafluorophenyl group) borine and the mass ratio that accounts for electrolyte gross mass be the VC of 2%, lithium salt is 1.1mol/L, and all the other, with embodiment 1, repeat no more here.
Comparative example 2
As different from Example 2, the mass content of nickel cobalt lithium aluminate (doping) is 95%, positive conductive agent is carbon black, and the mass content of positive conductive agent is 2.5%, the mass content of positive pole bonding agent is 2.5%, and not containing three (pentafluorophenyl group) borine in electrolyte, the concentration of lithium salts is 1.0mol/lL, all the other, with embodiment 2, repeat no more here.
Carry out capacity and charge-discharge test to the battery that embodiment 2 and comparative example 2 provide, rate of charge is set to 5C and 10C, acquired results in table 1, as can be seen from Table 1: battery of the present invention has higher density relative to comparative example 2 and promotes and charging rate lifting.
Cycle life test is carried out to the battery that embodiment 2 and comparative example 2 provide, circulation is set to the acceleration circulation that 10C charging/10C discharges, acquired results is in table 1, as can be seen from Table 1: battery of the present invention is in circulation after 1000 weeks, capacity still remains on more than 96%, the battery of comparative example 2 is then below 82%, and this shows that battery of the present invention has better high rate charge-discharge characteristic.
Embodiment 3
As different from Example 1, positive active material is the mixture of cobalt acid lithium and LiMn2O4, and the mass ratio of the two is 5:1, and the mass content of positive active material is 99.2%, and wherein, the Surface coating of cobalt acid lithium has Al
2o
3layer, and Al
2o
3the ratio of the quality of the sour lithium of quality and cobalt of layer is 1:100, and LiMn2O4 is then the Zr of 0.3% doped with mass percent; Positive conductive agent is the mixture of carbon nano-tube and Graphene, and the mass content of carbon nano-tube is 0.1%, and the mass content of Graphene is 0.1%; Positive pole bonding agent is polyvinyl alcohol, and the mass content of positive pole bonding agent is 0.6%; Additive comprise the mass ratio accounting for electrolyte gross mass be 0.5% pentafluorophenyl group boron oxalate and the mass ratio that accounts for electrolyte gross mass be the VC of 2%, lithium salt is 1.15mol/L, and all the other, with embodiment 1, repeat no more here.
Comparative example 3
As different from Example 3, the mass content of positive active material is 95%, and wherein, the surface of cobalt acid lithium is not coated, and LiMn2O4 does not then carry out doping treatment; Positive conductive agent is carbon black, and the mass content of positive conductive agent is 2.5%, and the mass content of positive pole bonding agent is 2.5%, and not containing pentafluorophenyl group boron oxalate in electrolyte, the concentration of lithium salts is 1.0mol/lL, and all the other, with embodiment 3, repeat no more here.
Carry out capacity and charge-discharge test to the battery that embodiment 3 and comparative example 3 provide, rate of charge is set to 5C and 10C, acquired results in table 1, as can be seen from Table 1; Battery of the present invention has higher density lifting and charging rate lifting compared to the battery of comparative example 3.
Cycle life test is carried out to the battery that embodiment 3 and comparative example 3 provide, circulation is set to the acceleration circulation that 10C charging/10C discharges, acquired results is in table 1, as can be seen from Table 1: battery of the present invention is in circulation after 1000 weeks, capacity still remains on about 97%, the battery of comparative example 3 is then below 89%, and this shows that battery of the present invention has better high rate charge-discharge characteristic.
Embodiment 4
As different from Example 1, positive active material is the mixture of cobalt acid lithium and nickle cobalt lithium manganate, the mass ratio of the two is 2:1, and the mass content of positive active material is 99%, wherein the Surface coating of cobalt acid lithium has TiO2 layer, and the ratio of the quality of the quality of TiO2 layer and cobalt acid lithium is 0.5:100; Positive conductive agent is the mixture of carbon black and carbon fiber, and the mass content of carbon black is 0.1%, and the mass content of carbon fiber is 0.2%; Positive pole bonding agent is polyvinyl alcohol, and the mass content of positive pole bonding agent is 0.7%; Additive comprise the mass ratio accounting for electrolyte gross mass be 0.7% pentafluorophenyl group boron oxalate and the mass ratio that accounts for electrolyte gross mass be the VC of 2%, lithium salt is 1.25mol/L, negative electrode active material is the mixture of native graphite and Delanium, the mass ratio of the two is 1:1, negative pole bonding agent is sodium alginate, cathode conductive agent is the mixture of Graphene and conductive black, and the mass ratio of the two is 1:4, negative pole stabilizer is hydroxypropyl methylcellulose sodium, all the other, with embodiment 1, repeat no more here.
Comparative example 4
As different from Example 4: the mass content of positive active material is 97.5%, the surface of cobalt acid lithium is not coated, positive conductive agent is carbon black, and the mass content of positive conductive agent is 1.5%, the mass content of positive pole bonding agent is 1%, not containing pentafluorophenyl group boron oxalate in electrolyte, the concentration of lithium salts is 1.0mol/lL, cathode conductive agent is carbon black, and all the other, with embodiment 4, repeat no more here.
Carry out capacity and charge-discharge test to the battery that embodiment 4 and comparative example 4 provide, rate of charge is set to 5C and 10C, and acquired results is in table 1; As can be seen from Table 1: battery of the present invention has higher density lifting and charging rate lifting compared to the battery of comparative example 4.
Cycle life test is carried out to the battery that embodiment 4 and comparative example 4 provide, circulation is set to the acceleration circulation that 10C charging/10C discharges, acquired results is in table 1, as can be seen from Table 1: battery of the present invention is in circulation after 1000 weeks, capacity still remains on more than 95%, the battery of comparative example 4 is then below 84%, and this shows that battery of the present invention has better high rate charge-discharge characteristic.
Embodiment 5
As different from Example 1, positive active material is LiMn2O4, and the mass content of positive active material is 99.5%; Positive conductive agent is the mixture of carbon black and phosphorus shape graphite, and the mass content of carbon black is 0.1%, and the mass content of phosphorus shape graphite is 0.1%; Positive pole bonding agent is butadiene-styrene rubber, and the mass content of positive pole bonding agent is 0.3%; Additive comprise the mass ratio accounting for electrolyte gross mass be 1.2% 12-crown ether-4 and the mass ratio that accounts for electrolyte gross mass be the PS of 2%, lithium salt is 1.3mol/L, negative electrode active material is the mixture of MCMB and soft carbon, the mass ratio of the two is 3:1, negative pole bonding agent is Kynoar, cathode conductive agent is the mixture of carbon fiber and conductive black, and the mass ratio of the two is 1:4, negative pole stabilizer is sodium cellulose glycolate, all the other, with embodiment 1, repeat no more here.
Comparative example 5
As different from Example 5: the mass content of positive active material is 96%, positive conductive agent is carbon black, and the mass content of positive conductive agent is 1%, the mass content of positive pole bonding agent is 3%, not containing 12-crown ether-4 in electrolyte, the concentration of lithium salts is 1.0mol/lL, and cathode conductive agent is carbon black, all the other, with embodiment 5, repeat no more here.
Carry out capacity and charge-discharge test to the battery that embodiment 5 and comparative example 5 provide, rate of charge is set to 5C and 10C, and acquired results is in table 1; As can be seen from Table 1: battery of the present invention has higher density lifting and charging rate lifting compared to the battery of comparative example 5.
Cycle life test is carried out to the battery that embodiment 5 and comparative example 5 provide, circulation is set to the acceleration circulation that 10C charging/10C discharges, acquired results is in table 1, as can be seen from Table 1: battery of the present invention is in circulation after 1000 weeks, capacity still remains on more than 97%, the battery of comparative example 5 is then below 87%, and this shows that battery of the present invention has better high rate charge-discharge characteristic.
In order to verify whether the positive pole diaphragm of battery in each embodiment and comparative example exists the problem of demoulding, disassembled by the battery after the acceleration circulation of 1000 times, observe the situation whether its positive plate exists demoulding, acquired results is in table 1.
Table 1: the performance test results of the battery that embodiment 1 to 5 and comparative example 1 to 5 provide.
It should be noted that, in table 1, the Calculation Basis of the energy density lifting percentage of embodiment 1 is comparative example 1, namely the energy density of embodiment 1 promotes energy density × 100% of percentage=(energy density of the energy density-comparative example 1 of embodiment 1)/comparative example 1, the rest may be inferred by analogy for it, that is, the Calculation Basis of the energy density lifting percentage of embodiment 2 is comparative examples 2, the Calculation Basis of the energy density lifting percentage of embodiment 3 is comparative examples 3, the Calculation Basis of the energy density lifting percentage of embodiment 4 is comparative examples 4, the Calculation Basis of the energy density lifting percentage of embodiment 5 is comparative examples 5.
In addition, positive conductive agent in embodiment 1 is also changed into the carbon black of 0.7% by the present inventor, found that this battery is after the acceleration circulation of 500 times, just there is the phenomenon come off in positive pole diaphragm, this shows, the present invention by use one dimension/two-dimentional electric conducting material or one dimension/two-dimentional electric conducting material mixed as conductive agent with zero dimension material carbon black, can ensure that diaphragm does not come off while reduction bonding agent consumption, the positive active material particle this is because conductive agent of the present invention can be connected better, thus play the effect of similar binding agent, and then suitably can reduce the content of bonding agent, improve activity substance content, promote energy density.
To sum up, the present invention under the prerequisite ensureing diaphragm not demoulding, can both improve the energy density of battery, improved again its high rate charge-discharge characteristic and improved charging rate.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a lithium ion battery, comprises positive plate, negative plate, is arranged at intervals at barrier film between described positive plate and described negative plate, and electrolyte, it is characterized in that:
Described positive plate comprises plus plate current-collecting body and is arranged at the positive electrode active material layer of described anode collection surface, and by mass percentage, described positive electrode active material layer comprises following component:
Positive active material 98.1% ~ 99.8%;
Positive conductive agent 0.1% ~ 1%;
Positive pole bonding agent 0.1% ~ 1%;
Described positive conductive agent is at least one in carbon fiber, carbon nano-tube, carbon nano rod and Graphene, or is the mixture of at least one in carbon fiber, carbon nano-tube, carbon nano rod, phosphorus shape graphite, Graphene and carbon black.
2. lithium ion battery according to claim 1, is characterized in that: described negative plate comprises negative current collector and is arranged at the negative electrode active material layer of described negative pole currect collecting surface, and by mass percentage, described negative electrode active material layer comprises following component:
Negative electrode active material 80% ~ 97%;
Cathode conductive agent 1% ~ 18%;
Negative pole bonding agent 1% ~ 18%;
Negative pole stabilizer 1% ~ 18%.
3. lithium ion battery according to claim 1, is characterized in that: described positive active material is at least one in nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, cobalt acid lithium, lithium nickelate and LiFePO4.
4. lithium ion battery according to claim 3, it is characterized in that: the percentage by weight that described positive active material doping quality accounts for active material is the metallic element of 0.1%-1%, and described metallic element is selected from least one in Mg, Zr, Ti, Zn, V and Cr.
5. lithium ion battery according to claim 3, is characterized in that: the Surface coating of described positive active material has oxide cladding layers or carbon-coating, and described oxide cladding layers is selected from Al
2o
3, ZrO
2, Y
2o
3, MgO and TiO
2in at least one, the ratio of the quality of described oxide cladding layers or described carbon-coating and the quality of described positive active material is (0.1-2): 100.
6. lithium ion battery according to claim 1, is characterized in that: described negative electrode active material is at least one in Delanium, native graphite, carbonaceous mesophase spherules, soft carbon, hard carbon, silicon, silicon dioxide and ashbury metal.
7. lithium ion battery according to claim 2, is characterized in that: described negative pole bonding agent and described positive pole bonding agent are at least one in Kynoar, butadiene-styrene rubber, sodium alginate, polyvinyl alcohol and polytetrafluoroethylene.
8. lithium ion battery according to claim 1, is characterized in that: described negative pole stabilizer is at least one in sodium carboxymethylcellulose, hydroxypropyl methylcellulose sodium and sodium cellulose glycolate; Described cathode conductive agent is carbon black, or is at least one in carbon fiber, carbon nano-tube, carbon nano rod and Graphene, or is the mixture of at least one in carbon fiber, carbon nano-tube, carbon nano rod, phosphorus shape graphite, Graphene and carbon black.
9. lithium ion battery according to claim 1, is characterized in that: described electrolyte comprises organic solvent, additive and lithium salts, and described additive comprises at least one in 12-crown ether-4, three (pentafluorophenyl group) borine and pentafluorophenyl group boron oxalate.
10. lithium ion battery according to claim 9, is characterized in that: the concentration of described lithium salts is 1.0-1.3mol/L.
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|---|---|---|---|
| CN201410542073.3A CN104362346A (en) | 2014-10-14 | 2014-10-14 | Lithium ion battery |
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|---|---|---|---|
| CN201410542073.3A CN104362346A (en) | 2014-10-14 | 2014-10-14 | Lithium ion battery |
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| CN105118989A (en) * | 2015-07-07 | 2015-12-02 | 湖南杉杉新材料有限公司 | Lithium ion battery lithium cobaltate positive electrode material and preparation method thereof |
| CN105633340A (en) * | 2015-12-17 | 2016-06-01 | 佛山市南海区欣源电子有限公司 | Composite pole plate of lithium ion battery and preparation method of composite pole plate |
| CN105932325A (en) * | 2016-07-18 | 2016-09-07 | 上海空间电源研究所 | Long-storage life lithium ion storage battery |
| CN106450430A (en) * | 2016-11-01 | 2017-02-22 | 江苏海四达电源股份有限公司 | Low temperature multiplying power type lithium ion battery |
| CN107331852A (en) * | 2017-08-10 | 2017-11-07 | 河北省科学院能源研究所 | Nickel-cobalt-manganese ternary combination electrode material of improved oxide surface cladding and preparation method thereof |
| CN108539138A (en) * | 2018-03-02 | 2018-09-14 | 广东邦普循环科技有限公司 | A kind of lithium ion anode material and preparation method thereof and lithium ion battery |
| CN109585779A (en) * | 2018-10-30 | 2019-04-05 | 福建冠城瑞闽新能源科技有限公司 | Take into account the lithium ion cell electrode piece and preparation method of energy density and power density |
| CN109698380A (en) * | 2018-12-28 | 2019-04-30 | 天能电池(芜湖)有限公司 | A kind of high-capacity lithium ion power battery and its material preparation process |
| CN109713274A (en) * | 2018-12-28 | 2019-05-03 | 天能电池(芜湖)有限公司 | A kind of high-capacity lithium ion power battery and preparation method thereof |
| CN109755557A (en) * | 2019-01-04 | 2019-05-14 | 桑顿新能源科技有限公司 | A kind of safe high-voltage high-energy-density lithium ion battery and preparation method thereof |
| CN112151742A (en) * | 2020-09-25 | 2020-12-29 | 福建师范大学 | Preparation method of ternary cathode material modified by metal oxide and graphene and used for improving performance of full battery |
| CN112582667A (en) * | 2020-04-04 | 2021-03-30 | 骆驼集团武汉新能源科技有限公司 | High-power lithium ion battery for automobile start-stop power supply |
| CN112786846A (en) * | 2019-11-08 | 2021-05-11 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN113013416A (en) * | 2021-03-22 | 2021-06-22 | 河南省特种设备安全检测研究院 | Explosion-proof forklift lithium battery and preparation method thereof |
| CN113130890A (en) * | 2019-12-31 | 2021-07-16 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105118989A (en) * | 2015-07-07 | 2015-12-02 | 湖南杉杉新材料有限公司 | Lithium ion battery lithium cobaltate positive electrode material and preparation method thereof |
| CN105633340A (en) * | 2015-12-17 | 2016-06-01 | 佛山市南海区欣源电子有限公司 | Composite pole plate of lithium ion battery and preparation method of composite pole plate |
| CN105932325A (en) * | 2016-07-18 | 2016-09-07 | 上海空间电源研究所 | Long-storage life lithium ion storage battery |
| CN106450430A (en) * | 2016-11-01 | 2017-02-22 | 江苏海四达电源股份有限公司 | Low temperature multiplying power type lithium ion battery |
| CN107331852B (en) * | 2017-08-10 | 2019-08-27 | 河北省科学院能源研究所 | The nickel-cobalt-manganese ternary combination electrode material and preparation method thereof of improved oxide surface cladding |
| CN107331852A (en) * | 2017-08-10 | 2017-11-07 | 河北省科学院能源研究所 | Nickel-cobalt-manganese ternary combination electrode material of improved oxide surface cladding and preparation method thereof |
| CN108539138A (en) * | 2018-03-02 | 2018-09-14 | 广东邦普循环科技有限公司 | A kind of lithium ion anode material and preparation method thereof and lithium ion battery |
| CN109585779A (en) * | 2018-10-30 | 2019-04-05 | 福建冠城瑞闽新能源科技有限公司 | Take into account the lithium ion cell electrode piece and preparation method of energy density and power density |
| CN109698380A (en) * | 2018-12-28 | 2019-04-30 | 天能电池(芜湖)有限公司 | A kind of high-capacity lithium ion power battery and its material preparation process |
| CN109713274A (en) * | 2018-12-28 | 2019-05-03 | 天能电池(芜湖)有限公司 | A kind of high-capacity lithium ion power battery and preparation method thereof |
| CN109755557A (en) * | 2019-01-04 | 2019-05-14 | 桑顿新能源科技有限公司 | A kind of safe high-voltage high-energy-density lithium ion battery and preparation method thereof |
| CN112786846A (en) * | 2019-11-08 | 2021-05-11 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN112786846B (en) * | 2019-11-08 | 2022-08-19 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN113130890A (en) * | 2019-12-31 | 2021-07-16 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN113130890B (en) * | 2019-12-31 | 2023-01-17 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN112582667A (en) * | 2020-04-04 | 2021-03-30 | 骆驼集团武汉新能源科技有限公司 | High-power lithium ion battery for automobile start-stop power supply |
| CN112151742A (en) * | 2020-09-25 | 2020-12-29 | 福建师范大学 | Preparation method of ternary cathode material modified by metal oxide and graphene and used for improving performance of full battery |
| CN115020638A (en) * | 2021-03-05 | 2022-09-06 | 珠海冠宇电池股份有限公司 | Lithium ion battery |
| CN115020638B (en) * | 2021-03-05 | 2023-06-09 | 珠海冠宇电池股份有限公司 | Lithium ion battery |
| CN113013416A (en) * | 2021-03-22 | 2021-06-22 | 河南省特种设备安全检测研究院 | Explosion-proof forklift lithium battery and preparation method thereof |
| CN113013416B (en) * | 2021-03-22 | 2024-02-20 | 河南省特种设备安全检测研究院 | Explosion-proof forklift lithium battery and preparation method thereof |
| CN114514642A (en) * | 2021-03-30 | 2022-05-17 | 宁德新能源科技有限公司 | Carbon current collector and electrochemical device |
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