CN106159236A - A kind of quick charge lithium titanate composite negative pole pole piece and lithium ion battery - Google Patents
A kind of quick charge lithium titanate composite negative pole pole piece and lithium ion battery Download PDFInfo
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention discloses a kind of quick charge lithium titanate composite negative pole pole piece and lithium ion battery.Described lithium titanate composite negative pole pole piece includes negative current collector, and the one or both sides of described negative current collector are sequentially provided with lithium titanate composite bed and mend lithium layer along the direction away from negative current collector；Described lithium titanate composite bed contains lithium titanate, Graphene and CNT, and lithium titanate, Graphene are (90～94) with the mass ratio of CNT: (1～3): (1～3)；Described benefit lithium layer comprises organolithium.This composite negative pole pole piece presents layer structure, and in lithium titanate composite bed, CNT and the Graphene of doping have the advantages that conductivity is high, load electric current is big, and rely on the feature that lithium titanate particle is little, transmission range is little, reduce the transmission time of lithium ion；Mending lithium layer and provide the lithium ion of abundance for battery in charge and discharge process, improve the transfer rate of lithium ion in battery, thus improve cycle performance and the high rate performance of battery, quick charge is effective.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of quick charge lithium titanate composite negative pole pole piece,
Also relate to a kind of lithium ion battery using this quick charge lithium titanate composite negative pole pole piece.
Background technology
Lithium ion battery is a kind of Novel energy storage apparatus grown up in recent years, and is widely used in digital domain, storage
Energy field, electric automobile field and quick charge field of tool thereof.Along with Fast Charge Battery demand was carried by market in recent years
High, it is desirable to lithium ion battery has the characteristic that charging rate is fast, high rate performance is good, security performance is high, and uses graphite-like at present
Negative material cannot meet the demand of lithium ion battery negative material, it is therefore desirable to develops other class negative material with full
The demand of foot quick charge lithium ion battery.
Lithium titanate anode material is with high (about 1.55V, the vs Li/Li of its intercalation potential+), charge and discharge process will not separate out
Li dendrite, security performance is good；In charge and discharge process, there is any change in material structure hardly, is a kind of " zero strain " material,
Good cycle；Lithium ion electrochemical diffusion coefficient an order of magnitude higher than graphite, is suitable for fast charging and discharging；Charging/discharging voltage is put down
Surely, platform voltage capacity exceedes the 90% of total capacity and becomes the first-selection of negative material used by quick charge lithium ion battery.
But, owing to quick charge (big multiplying power) is crossed, range request lithium ion transport speed is high, quantity is many, and directly uses titanium
Acid lithium titanate cathode material can cause the lazy weight of lithium ion in negative material, causes the hysteresis quality of lithium ion transport, has affected fast
Fill effect.
In prior art, CN105336914A discloses the rich lithium cathode sheet of a kind of lithium rechargeable battery, including negative pole
Collector and negative electrode active material layer, negative electrode active material layer contains negative electrode active material and is coated in the table of negative current collector
Face；Described negative electrode active material layer is away from being coated with containing lithium pulp layer on the surface of negative current collector, described containing lithium pulp layer bag
Include dispersant, conductive agent, lithium metal powder and non-aqueous organic solvent, wherein non-aqueous organic solvent and lithium rechargeable battery
Electrolyte dissolves each other.Negative electrode active material in described negative electrode active material layer is selected from graphite, silicon, SiOx (0 < x < 2)
Plant or several.
As it has been described above, negative pole of the prior art to mend lithium many for carbon back, elemental silicon or silica type negative material, due to
In contrast, the highest an order of magnitude of lithium ion electrochemical diffusion coefficient, applicable fast charging and discharging, is negative with lithium titanate to lithium titanate
The negative pole of the fast charging and discharging lithium ion battery of pole material main component is mended lithium technology and is had no report.
Summary of the invention
It is an object of the invention to provide a kind of quick charge lithium titanate composite negative pole pole piece, lithium ion transport speed is high, soon
Fill effective.
Second object of the present invention is to provide a kind of lithium ion battery using composite negative pole pole piece.
In order to realize object above, the technical solution adopted in the present invention is:
A kind of quick charge lithium titanate composite negative pole pole piece, including negative current collector, the one side of described negative current collector or
Two sides is sequentially provided with lithium titanate composite bed and mends lithium layer along the direction away from negative current collector；Described lithium titanate composite bed mainly by
Lithium titanate, Graphene, CNT and binding agent composition, lithium titanate, Graphene are (90～94) with the mass ratio of CNT:
(1～3): (1～3)；Described benefit lithium layer comprises organolithium.
The quick charge lithium titanate composite negative pole pole piece of the present invention presents layer structure, the one or both sides of negative current collector
It is sequentially provided with lithium titanate composite bed along the direction away from negative current collector and mends lithium layer, the CNT adulterated in lithium titanate and stone
Ink alkene has the advantages that conductivity is high, load electric current is big, and relies on the feature that lithium titanate particle is little, transmission range is little, reduces
The transmission time of lithium ion；Mend lithium layer simultaneously and the lithium ion of abundance is provided for battery in charge and discharge process, therefore improve battery
The transfer rate of middle lithium ion, thus improve cycle performance and the high rate performance of battery, quick charge is effective.
Described lithium titanate composite bed is (60～200) with the thickness ratio of benefit lithium layer: (1～5).
Described benefit lithium layer is mainly made up of organolithium and binding agent, and organolithium is (90～95) with the mass ratio of binding agent:
(5～10).Preferably, mending the binding agent used by lithium layer is Kynoar.
Described organolithium is any one or combination in n-BuLi, tert-butyl lithium, phenyl lithium.
Described negative current collector is netted Copper Foil, and thickness is 10～20 μm, and porosity is 40%～60%.This composite negative pole
Pole piece utilizes the feature that reticulated collectors porosity is high, provides express passway for the transmission of lithium ion in charge and discharge process.
Described lithium titanate is nano lithium titanate, and particle diameter is 50～500nm.
Described lithium titanate composite bed, lithium titanate is (90～94) with the mass ratio of binding agent: (4～8).Preferably, described
Binding agent used by lithium titanate composite bed is Kynoar.
Described quick charge lithium titanate composite negative pole pole piece, along the direction away from negative current collector, mends the outside of lithium layer
Being additionally provided with meta-aluminic acid lithium layer, described benefit lithium layer is (1～5) with the thickness ratio of meta-aluminic acid lithium layer: (5～10)；Described lithium metaaluminate
Layer is containing lithium metaaluminate.
Described meta-aluminic acid lithium layer is mainly by lithium metaaluminate (LiAlO2) and binding agent composition, lithium metaaluminate and the matter of binding agent
Amount ratio is (90～95): (5～10).Preferably, the binding agent used by described meta-aluminic acid lithium layer is Kynoar.
The preparation method of above-mentioned quick charge lithium titanate composite negative pole pole piece, comprises the following steps:
1) slurry preparation:
Lithium titanate slurry preparation: take binding agent and be dissolved in solvent, add Graphene, CNT and lithium titanate afterwards,
Mix homogeneously obtains lithium titanate slurry；
Mending lithium slurry preparation: take binding agent and be dissolved in solvent, add organolithium afterwards, mix homogeneously obtains mending lithium slurry
Material；
Lithium metaaluminate slurry preparation: taking binding agent and be dissolved in solvent, add lithium metaaluminate afterwards, mix homogeneously obtains partially
Lithium aluminate slurry；
2) preparation of composite negative pole pole piece:
Take negative current collector, after its one side or coated on both sides lithium titanate slurry, be dried and form lithium titanate composite bed；Exist again
Lithium titanate composite bed surface-coated mends lithium slurry, and dried formation mends lithium layer；Finally mending lithium layer surface-coated lithium metaaluminate slurry
Material, dried formation meta-aluminic acid lithium layer, obtain composite negative pole pole piece.
Preferably, solvent for use is N-Methyl pyrrolidone.
The quick charge lithium titanate composite negative pole pole piece of the present invention, arranges benefit lithium layer in cathode pole piece, at lithium titanate electricity
During pond carries out high rate charge-discharge, mend lithium ion in lithium layer and can supplement in charge and discharge process lithium ion quantity in time not
Foot, and express passway is provided, thus improve its high rate performance.
Prior art uses solid Copper Foil as collector, easily makes owing to lithium concentration is different between pole piece from pole piece
Become concentration difference, and the composite negative pole pole piece of the present invention use reticulated collectors, lithium ion can between different pole piece layer with
Meaning is mobile, reduces the concentration difference between pole piece, improves chemical property and the concordance of battery.
The quick charge lithium titanate composite negative pole pole piece of the present invention, is additionally provided with meta-aluminic acid lithium layer, partially in the outside mending lithium layer
Aluminic acid lithium layer can increase the transfer rate of lithium ion in charge and discharge process, lithium titanate can be avoided directly to connect with electrolyte simultaneously
Touch, reduce the Probability of lithium titanate side reaction and reduce its flatulence amount, during final reduction lithium titanate large current charge
Gas production, improves cycle performance and the high rate performance of battery further, and low-hanging fruit is good.
A kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, described negative pole uses above-mentioned quick charge
Lithium titanate composite negative pole pole piece.
The positive active material that described positive pole uses is nickel-cobalt-manganese ternary material.Preferably, described nickel-cobalt-manganese ternary material
For LiNi0.5Co0.2Mn0.3O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.8Co0.1Mn0.1O2In any one.
In described electrolyte, electrolyte is lithium hexafluoro phosphate (LiPF6), solvent is carbonate solvent.Lithium hexafluoro phosphate exists
Concentration in electrolyte is 1.0～1.3mol/L.Preferably, described carbonate solvent is ethylene carbonate (EC) and carbonic acid diethyl
The mixed solvent of ester (DEC).In described mixed solvent, ethylene carbonate (EC) is 1 with the mass ratio of diethyl carbonate (DEC):
1。
Preferably, described barrier film is Celgard 2400 film.
The lithium ion battery of the present invention, uses above-mentioned quick charge lithium titanate composite negative pole pole piece as negative pole, and this is multiple
Close cathode pole piece and improve the lithium ion content in cathode pole piece by mending lithium layer, thus improve high rate performance and the cyclicity of battery
Can, have and good fill effect soon, be suitable for promoting the use of.
Accompanying drawing explanation
Fig. 1 is the multiplying power charge graph of embodiment 1 gained lithium ion battery；
Fig. 2 is the multiplying power charge graph of comparative example gained lithium ion battery.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
In detailed description of the invention, lithium titanate used is nano lithium titanate, and particle diameter is 50～500nm.
Embodiment 1
The quick charge lithium titanate composite negative pole pole piece of the present embodiment, including negative current collector, described negative current collector
One or both sides are sequentially provided with lithium titanate composite bed, mend lithium layer and meta-aluminic acid lithium layer, metatitanic acid along the direction away from negative current collector
Lithium composite bed, benefit lithium layer are 200:3:8 with the thickness of meta-aluminic acid lithium layer；
Described negative current collector is netted Copper Foil, and thickness is 15 μm, and porosity is 50%；
The thickness of described lithium titanate composite bed is 200 μm, nano lithium titanate, Graphene, CNT and binding agent gather
Vinylidene forms, and nano lithium titanate, Graphene, CNT are 92:2:1:5 with the mass ratio of Kynoar；
The thickness of described benefit lithium layer is 3 μm, is made up of n-BuLi and binding agent Kynoar, and n-BuLi is inclined with poly-
The mass ratio of fluorothene is 92:8；
The thickness of described meta-aluminic acid lithium layer is 8 μm, is made up of lithium metaaluminate and binding agent Kynoar, lithium metaaluminate with
The mass ratio of Kynoar is 92:8.
The preparation method of the quick charge lithium titanate composite negative pole pole piece of the present embodiment, comprises the following steps:
1) slurry preparation:
Lithium titanate slurry preparation: take 5g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add 2g afterwards
Graphene and the CNT of 1g, after stirring, add the nano lithium titanate of 92g, stir 2h, obtain lithium titanate slurry
Material；
Mend lithium slurry preparation: take 8g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add 92g afterwards
N-BuLi, be uniformly mixing to obtain benefit lithium slurry；
Lithium metaaluminate slurry preparation: take 8g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add afterwards
The lithium metaaluminate of 92g, is uniformly mixing to obtain lithium metaaluminate slurry；
2) preparation of composite negative pole pole piece:
Take netted Copper Foil that thickness is 15 μm as negative current collector, by coating machine at its surface-coated lithium titanate slurry
After, it is dried and forms the lithium titanate composite bed that thickness is 200 μm；Mend lithium by flush coater in lithium titanate composite bed surface-coated again to starch
Material, dried formation thickness is the benefit lithium layer of 3 μm；Lithium layer surface-coated lithium metaaluminate slurry is being mended finally by flush coater, dry
Form the meta-aluminic acid lithium layer that thickness is 8 μm after dry, obtain composite negative pole pole piece.
The lithium ion battery of the present embodiment, including positive pole, negative pole, barrier film and electrolyte；Use above-mentioned gained composite negative pole
Pole piece is negative pole, uses nickel-cobalt-manganese ternary material (LiNi1/3Co1/3Mn1/3O2) it is that positive active material prepares positive pole, with LiPF6/
(EC, DEC volume ratio is 1:1, LiPF to EC+DEC6Concentration is 1.3mol/L) it is electrolyte, Celgard 2400 film is barrier film, group
Dress up the soft-package battery of 7Ah；It is charged with 0.1C multiplying power afterwards, constant-current charge to 3.2V, discharges generation in charging process
Gas, then with the multiplying power discharging of 0.1C to 1.0V, the gas row that will produce in battery charge and discharge process after charge and discharge cycles 2 times
Go out, i.e. obtain described lithium ion battery.
Embodiment 2
The quick charge lithium titanate composite negative pole pole piece of the present embodiment, including negative current collector, described negative current collector
One or both sides are sequentially provided with lithium titanate composite bed, mend lithium layer and meta-aluminic acid lithium layer, metatitanic acid along the direction away from negative current collector
Lithium composite bed, benefit lithium layer are 60:1:5 with the thickness of meta-aluminic acid lithium layer；
Described negative current collector is netted Copper Foil, and thickness is 10 μm, and porosity is 60%；
The thickness of described lithium titanate composite bed is 60 μm, poly-partially by nano lithium titanate, Graphene, CNT and binding agent
Fluorothene forms, and nano lithium titanate, Graphene, CNT are 94:1:1:4 with the mass ratio of Kynoar；
The thickness of described benefit lithium layer is 1 μm, is made up of tert-butyl lithium and binding agent Kynoar, and tert-butyl lithium is inclined with poly-
The mass ratio of fluorothene is 95:5；
The thickness of described meta-aluminic acid lithium layer is 5 μm, is made up of lithium metaaluminate and binding agent Kynoar, lithium metaaluminate with
The mass ratio of Kynoar is 95:5.
The preparation method of the quick charge lithium titanate composite negative pole pole piece of the present embodiment, comprises the following steps:
1) slurry preparation:
Lithium titanate slurry preparation: take 4g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add 1g afterwards
Graphene and the CNT of 1g, after stirring, add the nano lithium titanate of 94g, stir 2h, obtain lithium titanate slurry
Material；
Mend lithium slurry preparation: take 5g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add 95g afterwards
N-BuLi, be uniformly mixing to obtain benefit lithium slurry；
Lithium metaaluminate slurry preparation: take 5g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add afterwards
The lithium metaaluminate of 95g, is uniformly mixing to obtain lithium metaaluminate slurry；
2) preparation of composite negative pole pole piece:
Take netted Copper Foil that thickness is 10 μm as negative current collector, by coating machine at its surface-coated lithium titanate slurry
After, it is dried and forms the lithium titanate composite bed that thickness is 60 μm；Mend lithium by flush coater in lithium titanate composite bed surface-coated again to starch
Material, dried formation thickness is the benefit lithium layer of 1 μm；Lithium layer surface-coated lithium metaaluminate slurry is being mended finally by flush coater, dry
Form the meta-aluminic acid lithium layer that thickness is 5 μm after dry, obtain composite negative pole pole piece.
The lithium ion battery of the present embodiment, using above-mentioned gained composite negative pole pole piece is negative pole, and remaining is with embodiment 1.
Embodiment 3
The quick charge lithium titanate composite negative pole pole piece of the present embodiment, including negative current collector, described negative current collector
One or both sides are sequentially provided with lithium titanate composite bed, mend lithium layer and meta-aluminic acid lithium layer, metatitanic acid along the direction away from negative current collector
Lithium composite bed, benefit lithium layer are 200:3:8 with the thickness of meta-aluminic acid lithium layer；
Described negative current collector is netted Copper Foil, and thickness is 20 μm, and porosity is 40%；
The thickness of described lithium titanate composite bed is 200 μm, nano lithium titanate, Graphene, CNT and binding agent gather
Vinylidene forms, and nano lithium titanate, Graphene, CNT are 90:1:1:8 with the mass ratio of Kynoar；
The thickness of described benefit lithium layer is 5 μm, is made up of phenyl lithium and binding agent Kynoar, phenyl lithium and polyvinylidene fluoride
The mass ratio of alkene is 90:10；
The thickness of described meta-aluminic acid lithium layer is 10 μm, is made up of lithium metaaluminate and binding agent Kynoar, lithium metaaluminate
It is 90:10 with the mass ratio of Kynoar.
The preparation method of the quick charge lithium titanate composite negative pole pole piece of the present embodiment, comprises the following steps:
1) slurry preparation:
Lithium titanate slurry preparation: take 8g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add 8g afterwards
Graphene and the CNT of 1g, after stirring, add the nano lithium titanate of 90g, stir 2h, obtain lithium titanate slurry
Material；
Mend lithium slurry preparation: take 10g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add 90g afterwards
N-BuLi, be uniformly mixing to obtain benefit lithium slurry；
Lithium metaaluminate slurry preparation: take 10g Kynoar and be dissolved in the N-Methyl pyrrolidone of 100ml, add afterwards
Enter the lithium metaaluminate of 90g, be uniformly mixing to obtain lithium metaaluminate slurry；
2) preparation of composite negative pole pole piece:
Take netted Copper Foil that thickness is 20 μm as negative current collector, by coating machine at its surface-coated lithium titanate slurry
After, it is dried and forms the lithium titanate composite bed that thickness is 200 μm；Mend lithium by flush coater in lithium titanate composite bed surface-coated again to starch
Material, dried formation thickness is the benefit lithium layer of 5 μm；Lithium layer surface-coated lithium metaaluminate slurry is being mended finally by flush coater, dry
Form the meta-aluminic acid lithium layer that thickness is 10 μm after dry, obtain composite negative pole pole piece.
The lithium ion battery of the present embodiment, using above-mentioned gained composite negative pole pole piece is negative pole, and remaining is with embodiment 1.
Comparative example
The lithium titanate anode pole piece of this comparative example is prepared by following methods: takes 5g Kynoar and is dissolved in 100ml
N-Methyl pyrrolidone in, add the Graphene of 2g and the CNT of 1g afterwards, after stirring, add receiving of 92g
Rice lithium titanate, stirs 2h, obtains lithium titanate slurry；Gained lithium titanate slurry is coated in the copper foil surface that thickness is 10 μm, dry
Form the lithium titanate composite bed that thickness is 100 μm after dry, obtain lithium titanate anode pole piece.
The lithium ion battery of comparative example, using above-mentioned gained cathode pole piece is negative pole, and remaining is with embodiment 1.
Experimental example 1 (half-cell test)
Respectively using embodiment 1-3 gained composite negative pole pole piece and comparative example gained cathode pole piece as positive pole, with lithium sheet it is
Negative pole, Celegard 2400 is barrier film, with LiPF6(solvent EC, DEC volume ratio is 1:1 to/EC+DEC, electrolyte LiPF6Concentration
For 1mol/L) it is electrolyte, it is below in the glove box of 0.1ppm being assembled into button cell at oxygen and water content, afterwards will button
Formula battery installs on blue electric tester, and with the rate charge-discharge of 0.1C, voltage range is 1.0V～2.8V, stops after circulating 3 weeks.
Test result is as shown in table 1.
Table 1 embodiment compares with the button cell of comparative example
| Object | Discharge capacity (mAH/g) first | Efficiency (%) first |
| Embodiment 1 | 175.5 | 99.8 |
| Embodiment 2 | 174.6 | 99.5 |
| Embodiment 3 | 172.8 | 99.4 |
| Comparative example | 153.4 | 94.7 |
As it can be seen from table 1 embodiment 1-3 gained lithium titanate composite negative pole pole piece gram volume and first in terms of efficiency bright
Show and be better than comparative example.Its reason is: be provided with benefit lithium layer in the lithium titanate composite negative pole pole piece of the present invention, provides for charge and discharge process
Sufficient lithium ion, improves the performance efficiency of its active substance, thus improves discharge capacity and the efficiency first of battery；At metatitanic acid
The outermost of lithium composite negative pole pole piece is additionally provided with meta-aluminic acid lithium layer, and lithium metaaluminate material has the spy that lithium ion transport speed is high
Point, improves the transfer rate of lithium ion in its charge and discharge process further, and the gram volume improving lithium titanate plays, thus enters one
Step improves discharge capacity and the efficiency first of battery.
Experimental example 2 (soft-package battery test)
1. cycle performance test
Example 1-3 and comparative example gained lithium ion battery (soft-package battery), with charge-discharge magnification as 2.0C/2.0C
Multiplying power carries out 1000 cycle performances test (test voltage scope: 1.5V-2.8V).Test result is as shown in table 2.
Table 2 embodiment compares with the cycle performance of comparative example
From table 2 it can be seen that the cycle performance of battery prepared by embodiment 1-3 is substantially better than comparative example.Its reason is: this
Containing mending lithium layer in the lithium titanate composite negative pole pole piece of invention, provide sufficient lithium ion for lithium ion battery charge and discharge process,
Thus improve its cycle performance.
2. high rate performance test
Example 1-3 and comparative example gained lithium ion battery (soft-package battery), test its high rate performance, charging/discharging voltage
Scope 1.5～2.8V, temperature 25 ± 3.0 DEG C, it is charged with 0.5C, 1.0C, 5.0C, 10.0C, 20.0C, puts with 0.5C
Electricity.Test result is as shown in table 3 and Fig. 1, Fig. 2.
Table 3 embodiment compares with the high rate performance of comparative example
From table 1 and Fig. 1, Fig. 2 it can be seen that the multiplying power charging performance of lithium ion battery prepared of embodiment 1-3 is the most excellent
In comparative example, i.e. the charging interval is shorter.Analysis reason is: needs the migration of lithium ion in lithium ion battery charging process, and mends
Containing sufficient lithium ion in lithium layer and outside meta-aluminic acid lithium layer, it is provided that enough lithium ions, thus shorten the charging interval,
Improve the multiplying power charging performance of battery.
3. thickness measuring
Example 1-3 and comparative example gained lithium ion battery (soft-package battery) carry out thickness measuring.First circulation is recorded
The thickness d 1 of front battery, then in the voltage range of 60 DEG C, 1.5～2.8V, charges with the multiplying power of 1.0C, and the multiplying power of 1.0C is put
Electricity is circulated test, again records the thickness d 2 of battery, calculate its thickness swelling (d2-d1)/d1 after circulating 500 times.Institute
4 must be the results are shown in Table.
Table 4 embodiment compares with the thickness change of comparative example
| Object | Thickness d 1 (cm) before circulation | Thickness d 2 (cm) after circulation | Expansion rate (%) |
| Embodiment 1 | 7.25 | 7.67 | 5.8 |
| Embodiment 2 | 7.23 | 7.67 | 6.1 |
| Embodiment 3 | 7.24 | 7.69 | 6.3 |
| Comparative example | 7.21 | 8.20 | 13.8 |
As can be seen from Table 4, the lithium ion battery that prepared by embodiment 1-3 thickness change in charge and discharge process is the least
In comparative example.Its reason is: containing mending lithium layer in the lithium titanate composite negative pole pole piece of the present invention, can avoid lithium titanate directly with
Electrolyte contacts, reduces the generation of side reaction；Meta-aluminic acid lithium layer is set in outermost simultaneously, lithium in charge and discharge process can be increased
The transfer rate of ion, meta-aluminic acid lithium layer can completely cut off again electrolyte and directly contacts with lithium titanate simultaneously, reduces lithium titanate and electricity
Solving the side reaction occurrence probability of liquid, when the most also reticulated collectors can also buffer and prevent lithium titanate from producing gas, local is swollen
The expansion of the swollen whole battery caused.Therefore, each part mentioned above cooperates, coordinative role, and gained lithium ion battery has good
Good high rate performance and cycle performance, and thickness change is little, combination property is high.
Claims (10)
1. a quick charge lithium titanate composite negative pole pole piece, it is characterised in that: include negative current collector, described negative current collector
One or both sides along being sequentially provided with lithium titanate composite bed away from the direction of negative current collector and mending lithium layer；Described lithium titanate is combined
Layer is mainly made up of lithium titanate, Graphene, CNT and binding agent, and lithium titanate, Graphene with the mass ratio of CNT are
(90～94): (1～3): (1～3)；Described benefit lithium layer comprises organolithium.
Quick charge lithium titanate composite negative pole pole piece the most according to claim 1, it is characterised in that: described lithium titanate is combined
Layer is (60～200) with the thickness ratio of benefit lithium layer: (1～5).
Quick charge lithium titanate composite negative pole pole piece the most according to claim 1 and 2, it is characterised in that: described benefit lithium layer
Mainly being made up of organolithium and binding agent, organolithium is (90～95) with the mass ratio of binding agent: (5～10).
Quick charge lithium titanate composite negative pole pole piece the most according to claim 3, it is characterised in that: described organolithium is just
Any one or combination in butyl lithium, tert-butyl lithium, phenyl lithium.
Quick charge lithium titanate composite negative pole pole piece the most according to claim 1, it is characterised in that: described negative current collector
For netted Copper Foil, thickness is 10～20 μm, and porosity is 40%～60%.
Quick charge lithium titanate composite negative pole pole piece the most according to claim 1, it is characterised in that: described lithium titanate is for receiving
Rice lithium titanate, particle diameter is 50～500nm.
Quick charge lithium titanate composite negative pole pole piece the most according to claim 1, it is characterised in that: along away from negative pole currect collecting
The direction of body, the outside mending lithium layer is additionally provided with meta-aluminic acid lithium layer, and described benefit lithium layer is (1～5) with the thickness ratio of meta-aluminic acid lithium layer:
(5～10)；Described meta-aluminic acid lithium layer contains lithium metaaluminate.
Quick charge lithium titanate composite negative pole pole piece the most according to claim 7, it is characterised in that: described meta-aluminic acid lithium layer
Mainly being made up of lithium metaaluminate and binding agent, lithium metaaluminate is (90～95) with the mass ratio of binding agent: (5～10).
9. a lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that: described negative pole uses such as right
Require the quick charge lithium titanate composite negative pole pole piece according to any one of 1-8.
Lithium ion battery the most according to claim 9, it is characterised in that: the positive active material that described positive pole uses is
Nickel-cobalt-manganese ternary material.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450481A (en) * | 2016-12-07 | 2017-02-22 | 清华大学深圳研究生院 | Lithium ion battery and preparation method thereof |
| CN106876689A (en) * | 2017-03-24 | 2017-06-20 | 中航锂电（洛阳）有限公司 | A kind of nitrogen-doped graphene silicon composite cathode material and preparation method thereof, lithium ion battery |
| CN107887607A (en) * | 2017-11-06 | 2018-04-06 | 陈和平 | A kind of lithium titanate composite pole piece and preparation method thereof, lithium battery |
| CN113346043A (en) * | 2021-06-04 | 2021-09-03 | 江西安驰新能源科技有限公司 | Low-temperature lithium ion battery positive pole piece and preparation method thereof, and lithium ion battery |
| CN114335428A (en) * | 2021-12-30 | 2022-04-12 | 重庆冠宇电池有限公司 | Positive plate, preparation method and battery |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117382A (en) * | 2013-02-25 | 2013-05-22 | 江苏乐能电池股份有限公司 | Lithium ion battery negative pole material capable of improving safety performance and preparation method thereof |
| WO2014119315A1 (en) * | 2013-01-31 | 2014-08-07 | 三洋電機株式会社 | Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| CN104752773A (en) * | 2015-04-01 | 2015-07-01 | 广东烛光新能源科技有限公司 | Preparation method of lithium ion battery |
| CN104766645A (en) * | 2015-03-24 | 2015-07-08 | 中国石油大学(北京) | Carbon nanotube-graphene composite electric conduction slurry and preparation method and application thereof |
-
2016
- 2016-08-26 CN CN201610740947.5A patent/CN106159236A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014119315A1 (en) * | 2013-01-31 | 2014-08-07 | 三洋電機株式会社 | Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| CN103117382A (en) * | 2013-02-25 | 2013-05-22 | 江苏乐能电池股份有限公司 | Lithium ion battery negative pole material capable of improving safety performance and preparation method thereof |
| CN104766645A (en) * | 2015-03-24 | 2015-07-08 | 中国石油大学(北京) | Carbon nanotube-graphene composite electric conduction slurry and preparation method and application thereof |
| CN104752773A (en) * | 2015-04-01 | 2015-07-01 | 广东烛光新能源科技有限公司 | Preparation method of lithium ion battery |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450481A (en) * | 2016-12-07 | 2017-02-22 | 清华大学深圳研究生院 | Lithium ion battery and preparation method thereof |
| CN106450481B (en) * | 2016-12-07 | 2019-06-04 | 清华大学深圳研究生院 | A kind of lithium ion battery and preparation method thereof |
| CN106876689A (en) * | 2017-03-24 | 2017-06-20 | 中航锂电（洛阳）有限公司 | A kind of nitrogen-doped graphene silicon composite cathode material and preparation method thereof, lithium ion battery |
| CN106876689B (en) * | 2017-03-24 | 2020-02-21 | 中航锂电（洛阳）有限公司 | Nitrogen-doped graphene-silicon composite negative electrode material, preparation method thereof and lithium ion battery |
| CN107887607A (en) * | 2017-11-06 | 2018-04-06 | 陈和平 | A kind of lithium titanate composite pole piece and preparation method thereof, lithium battery |
| CN114497468A (en) * | 2020-11-11 | 2022-05-13 | 比亚迪股份有限公司 | Lithium ion battery |
| CN114497468B (en) * | 2020-11-11 | 2023-07-14 | 比亚迪股份有限公司 | Lithium ion battery |
| CN113346043A (en) * | 2021-06-04 | 2021-09-03 | 江西安驰新能源科技有限公司 | Low-temperature lithium ion battery positive pole piece and preparation method thereof, and lithium ion battery |
| CN114335428A (en) * | 2021-12-30 | 2022-04-12 | 重庆冠宇电池有限公司 | Positive plate, preparation method and battery |
| CN114335428B (en) * | 2021-12-30 | 2024-01-30 | 重庆冠宇电池有限公司 | Positive plate, preparation method and battery |
| CN114583175A (en) * | 2022-04-28 | 2022-06-03 | 华中科技大学 | Porous graphene-doped and organic lithium salt-doped composite lithium supplement material and preparation method and application thereof |
| WO2024061011A1 (en) * | 2022-09-22 | 2024-03-28 | 华为技术有限公司 | Lithium-ion battery and electric device |
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