CN105118958A - Positive electrode plate and preparing method thereof and lithium ion battery - Google Patents
Positive electrode plate and preparing method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN105118958A CN105118958A CN201510494698.1A CN201510494698A CN105118958A CN 105118958 A CN105118958 A CN 105118958A CN 201510494698 A CN201510494698 A CN 201510494698A CN 105118958 A CN105118958 A CN 105118958A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- pole piece
- anode pole
- material layer
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a positive electrode plate and a preparing method thereof and a lithium ion battery. The positive electrode plate aims at solving the problems that for a positive electrode plate in the prior art, under the situation of high charging voltage, the battery circulation performance and the high-temperature storage performance are poor. The positive electrode plate comprises a positive electrode current collector and a positive electrode material layer attached to the surface of the positive electrode current collector. A poly-dopamine layer is further attached to the surface of the positive electrode material layer. Meanwhile, the invention discloses the preparing method of the positive electrode plate and the lithium ion battery with the positive electrode plate. The battery circulation performance and the high-temperature storage performance of the lithium ion battery prepared from the positive electrode plate are excellent under the situation of high changing voltage.
Description
Technical field
The present invention relates to a kind of anode pole piece and preparation method thereof, and comprise the lithium ion battery of this anode pole piece.
Background technology
Lithium rechargeable battery has high-energy-density, high cycle life, the features such as low self-discharge, and at mobile phone, panel computer, the consumer electronics products such as portable power source obtain and apply widely.In recent years, smart mobile phone ground fast development, the continuous increase of its function, for the lithium ion battery as its power source, comply with smart mobile phone ground growth requirement, its energy density is riseing gradually, and combination property is also continuous in raising.
Normally, as the positive electrode active materials of lithium rechargeable battery, generally select the material that can reversiblely carry out discharging and inserting lithium ion, as having general formula LiCo
xmn
yni
zo
2(wherein x+y+z=1) or LiMPO
4a kind of separately in the material of (in M=Fe, Mn, Co one or more) or mix the multiple positive electrode active materials as lithium ion battery.Current in consumer electronics product, mainly adopt LiCoO
2as positive electrode active materials.Meanwhile, in order to obtain higher energy density, obtained the rising of capacity by the charging upper limit voltage promoting battery.As cell voltage is brought up to 4.35V from 4.2V, discharge capacity of the cell can promote about 15%, if rise to 4.4V again, capacity is compared to 4.35V, and capacity can obtain the lifting of about about 6% further.But along with the raising of charging voltage, promote although energy density obtains, cycle performance of battery and high-temperature storage performance decline to some extent.
For overcoming the problems referred to above, a kind of anode pole piece is provided in prior art, anode pole piece forms inorganic particle layer, and combine separator (emptying aperture average pore size is 0.15 μm-0.3 μm) acting in conjunction with emptying aperture, certain lifting of high-temperature behavior can be obtained, but fundamentally do not overcome the problems referred to above, when long-time high-temperature storage, the above-mentioned successful that improves weakens.
Additionally provide a kind of method in prior art, by spraying at positive electrode surface or positive pole being immersed in Lithium carbonate solution, form protective layer, improve the high-temperature behavior (as high temperature circulation and high-temperature storage performance) of lithium ion battery with this.But the effect of the program is also not obvious.
Summary of the invention
Technical problem to be solved by this invention is for anode pole piece of the prior art under high charge voltage condition, and the problem of cycle performance of battery and high-temperature storage performance difference provides a kind of anode pole piece.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme:
A kind of anode pole piece is provided, comprises plus plate current-collecting body and the positive electrode material layer being attached to described anode collection surface; Described positive electrode material layer surface is also attached with poly-DOPA amine layer.
Meanwhile, present invention also offers the preparation method of above-mentioned anode pole piece, comprise the steps:
S1, acquisition anode pole piece precursor; Described anode pole piece precursor comprises plus plate current-collecting body and is attached to the positive electrode material layer of described anode collection surface;
S2, acquisition dopamine solution;
S3, the positive electrode material layer described dopamine solution be arranged on described anode pole piece precursor are surperficial, then dry, form poly-DOPA amine layer, obtain anode pole piece.
In addition, present invention also offers a kind of lithium ion battery, the electrolyte comprising battery container, be arranged at the battery core in battery container and fill in described battery container; Described battery core comprises the anode pole piece, barrier film and the cathode pole piece that set gradually; Described anode pole piece is aforesaid anode pole piece.
The present inventor is found by great many of experiments, under high charge voltage condition, the nonaqueous electrolytic solution adopted in lithium ion battery can be oxidized when contacting with high-voltage anode pole piece, and product may be deposited on anode pole piece surface, also there is part to pass barrier film, cathode pole piece reduces and forms deposit.Sedimental formation can hinder lithium ion the embedding at cathode pole piece place embedding go out.And increasing along with sediment yield, barrier film inside aperture can be caused blocked, thus hinder the migration of lithium ion, the cycle performance of deteriorated lithium ion battery.When lithium ion battery is under hot conditions, the problems referred to above are more obvious.
Inventor finds, if by forming inorganic particle layer on anode pole piece, catch the electrolyte oxidation catabolite occurring in positive electrode surface with inorganic particulate; Meanwhile, in conjunction with there is the separator of hole (average pore size is 0.15 μm-0.3 μm) to reduce the impact of oxidative degradation products.But said method does not fundamentally reduce the generation of oxidation product, therefore, said method is to the improvement DeGrain of cycle performance of battery and high-temperature storage performance.Further, under long-time high-temperature storage conditions, the effect of said method will weaken further.
And if pass through to form protective layer at anode pole piece surface spraying or dipping Lithium carbonate solution, the cycle performance of battery of lithium ion battery obtained thus and the improvement DeGrain of high-temperature storage performance.
In the present invention, by the auto polymerization of dopamine solution, poly-DOPA amine layer is formed on the positive electrode material layer surface of anode pole piece precursor, can effectively be covered in positive electrode material layer surface, thus reduce the oxidation Decomposition of electrolyte on anode pole piece widely, then decrease the migration amount of oxidation product to cathode pole piece, provide high temperature storing performance and the cycle performance of lithium ion battery significantly.
N group in poly-dopamine molecule has stronger complexing power to metal ion, can complexing positive electrode may the metal ion of stripping in pyroprocess, thus the free metal ion decreased in electrolyte, significantly avoid the phenomenon of metal ion cathodic reduction simultaneously.Meanwhile, poly-dopamine is to the compatible height of electrolyte, and affinity is good, to be easy to by electrolyte soak, especially in the positive plate of high compacted density, greatly can accelerate wetting to pole piece of electrolyte, thus contribute to cycle performance and the high rate performance of raising battery.Positive electrode surface covers polymeric membrane in addition, significantly reduces the generation of the particle detachment phenomenon that positive electrode surface particle occurs in preparation process.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 contrasts schematic diagram with high temperature 45 degree of cyclic curves of comparative example 1.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Anode pole piece provided by the invention comprises plus plate current-collecting body and is attached to the positive electrode material layer of described anode collection surface; Described positive electrode material layer surface is also attached with poly-DOPA amine layer.
According to the present invention, in above-mentioned anode pole piece, plus plate current-collecting body and the positive electrode material layer being attached to anode collection surface can adopt conventional various.
Such as, the kind of above-mentioned plus plate current-collecting body has been conventionally known to one of skill in the art, such as, can be selected from aluminium foil, Copper Foil, Punching steel strip.
Usually, positive electrode material layer comprises positive electrode active materials, positive electrode binder and positive conductive agent.In the present invention, the concrete material that above-mentioned positive electrode active materials, positive electrode binder and positive conductive agent adopt and relative amount can to adopt in prior art conventional, such as: described positive electrode active materials is selected from LiMn
2o
4, LiM
xfe
1-xpO
4, Li
1+al
1-b-cm
bn
co
2in one or more; Wherein, 0≤x≤1, M be selected from Mn, Ti, Co, V, Mg one or more; 0≤a≤0.2,0≤b≤1,0≤c≤1,0≤b+c≤1.0, L, M, N be in Co, Mn, Ni, Al, Mg, Ga, Sc, Ti, V, Cr, Fe, Cu and Zn one or more.Such as, specifically LiFePO can be adopted
4, Li
3v
2(PO
4)
3, LiMn
2o
4, LiMnO
2, LiNiO
2, LiNiCoMnO
2, LiNi
0.85co
0.1al
0.05o
2, LiCoO
2in one or more.
The present invention is not particularly limited described positive conductive agent, can be the positive conductive agent of this area routine, at least one in such as acetylene black, carbon nano-tube, HV, vapour deposition carbon fiber, Graphene, carbon black.Wherein, with the weight of positive active material for benchmark, the content of described conductive agent is 0.1-20wt%, is preferably 0.5-10wt%.
The kind of described positive electrode binder and content are conventionally known to one of skill in the art, and such as fluorine resin and polyolefin compound are as one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).In general, according to the difference of positive electrode binder kind used, with the weight of positive active material for benchmark, the content of positive electrode binder is 0.01-10wt%, is preferably 0.02-5wt%.
The thickness of the positive electrode material layer on above-mentioned plus plate current-collecting body can change in a big way, and under preferable case, the thickness of described positive electrode material layer is 30-200 μm.
According to the present invention, be also attached with poly-DOPA amine layer on above-mentioned positive electrode material layer surface, by this poly-DOPA amine layer, the cycle performance of battery under high charge voltage condition and high-temperature storage performance can be improved greatly.
The thickness of above-mentioned poly-DOPA amine layer can change in a big way, and for ensureing the ionic conductivity of battery and cycle performance and high-temperature storage performance simultaneously, under preferable case, the thickness of described poly-DOPA amine layer is 0.005-2 μm.
Meanwhile, present invention also offers the preparation method of above-mentioned anode pole piece, specifically comprise the steps:
S1, acquisition anode pole piece precursor; Described anode pole piece precursor comprises plus plate current-collecting body and is attached to the positive electrode material layer of described anode collection surface;
S2, acquisition dopamine solution;
S3, the positive electrode material layer described dopamine solution be arranged on described anode pole piece precursor are surperficial, then dry, form poly-DOPA amine layer, obtain anode pole piece.
According to the present invention, first, anode pole piece precursor is prepared.In the present invention, above-mentioned anode pole piece precursor can adopt anode pole piece of the prior art.Its preparation method is known in the field, such as, is coated in by anode sizing agent on plus plate current-collecting body, and drying, calendering prepare.Wherein, anode sizing agent comprises positive electrode active materials, positive conductive agent, positive electrode binder and positive pole solvent.
Above-mentioned positive electrode active materials, positive conductive agent, material that positive electrode binder adopts and respective addition as mentioned before, do not repeat them here.Above-mentioned positive pole solvent is used for positive electrode active materials, positive conductive agent, positive electrode binder to be distributed in wherein, forms pulp-like, is beneficial to coating.In follow-up dry run, above-mentioned positive pole solvent is removed.The concrete material that positive pole solvent adopts and addition are that those skilled in the art known, and do not repeat them here.
Under preferable case, in the anode pole piece precursor of acquisition, the thickness of positive electrode material layer is 30-200 μm.
As step S2, in the present invention, also need to obtain dopamine solution.According to the present invention, under preferable case, in described dopamine solution, the concentration of dopamine is 0.1-1000mg/mL.For ensureing effectively can to form poly-DOPA amine layer on positive electrode material layer surface, and ensure the ionic conductivity of anode pole piece, the concentration being more preferably dopamine is 0.5-500mg/mL.
Meanwhile, in the present invention, the above-mentioned dopamine solution provided is for the formation of surperficial in positive electrode material layer, and form required poly-DOPA amine layer, therefore, under preferable case by the dopamine auto polymerization in dopamine solution, the pH value of above-mentioned dopamine solution is 7.5-10, more preferably 8-9.
According to the present invention, as step S3, described dopamine solution need be arranged at the positive electrode material layer surface on described anode pole piece precursor, then dry, form poly-DOPA amine layer.
Concrete, by positive electrode material layer surface described in described dopamine solution dipping or spray treatment.
Wherein, when adopting dopamine solution to flood above-mentioned anode pole piece precursor, under preferable case, dip time is 1-3600s.For avoiding the anode pole piece sclerosis causing because dip time is long preparing, under further preferable case, dip time is 10-1000s.
The thickness of the poly-DOPA amine layer of formation is directly had influence in the number of the amount of the dopamine solution of positive electrode material layer surface impregnation or spraying, in the present invention, under preferable case, by controlling the amount of the dopamine solution in positive electrode material layer surface impregnation or spraying, the thickness making the poly-DOPA amine layer formed on positive electrode material layer surface is 0.005-2 μm.
The concrete technology of above-mentioned dipping or spraying and method are known in the art, repeat no more in the present invention.
In addition, present invention also offers a kind of lithium ion battery, the electrolyte comprising battery container, be arranged at the battery core in battery container and fill in described battery container; Described battery core comprises the anode pole piece, barrier film and the cathode pole piece that set gradually; Described anode pole piece is foregoing anode pole piece.
For above-mentioned lithium ion battery, cathode pole piece and barrier film also can adopt known in the art.Such as, described cathode pole piece comprises negative current collector and is attached to the negative material on negative current collector.
The present invention does not limit for the negative current collector adopted, negative active core-shell material, cathode conductive agent and negative electrode binder, can adopt various material of the prior art.Such as, described negative active core-shell material is selected from one or more in graphite (such as native graphite, Delanium), petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, silicon alloy, is preferably Delanium or native graphite.Cathode conductive agent be selected from acetylene black, carbon nano-tube, Graphene, carbonyl nickel powder, copper powder, iron powder, zinc powder or aluminium powder one or more.Described negative electrode binder is selected from one or more in polytetrafluoroethylene, Kynoar, carboxymethyl cellulose, butadiene-styrene rubber, silane coupler, titanate coupling agent, hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, methylcellulose, polyacrylic acid.Described negative electrode binder also can form jelly with negative pole solvent, and described negative pole solvent is selected from one or more in water, acetone, 1-METHYLPYRROLIDONE, oxolane, dimethyl sulfoxide (DMSO), methylethylketone, ethyl acetate.
The various negative current collectors that negative current collector is known to the skilled person, such as, negative current collector can be Copper Foil.
In lithium ion battery disclosed by the invention, anode pole piece is that method disclosed by the invention prepares, cathode pole piece prepares by existing method, such as above-mentioned negative active core-shell material, cathode conductive agent and negative electrode binder are mixed in mass ratio, add negative pole solvent even, be coated on negative current collector, dry, after roll-in, die-cut.
Lithium ion battery miscellaneous part, it is conventional that such as battery container, barrier film, electrolyte etc. are this area, not restriction.
According to the present invention, described barrier film is arranged between anode pole piece and cathode pole piece, has electrical insulation capability, and ionic conduction performance and liquid keep function.Described barrier film can be selected from various barrier films used in lithium ion battery, as polyolefin micro porous polyolefin membrane, polyimide porous membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper and modification composite diaphragm are as the ceramic diaphragm of surface-coated ceramic powder, or surface-coated polymeric membrane is as PVDF (Kynoar), the composite diaphragm etc. of PVDF-HFP (Kynoar-hexafluoropropylene).The position of described barrier film, character and kind are conventionally known to one of skill in the art.
In the present invention, described electrolyte comprises electrolyte lithium salt and nonaqueous solvents.
Described lithium salts be selected from lithium perchlorate, lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two trifluoromethanesulfonimide lithium, trifluoromethyl sulfonic acid lithium one or more; Described nonaqueous solvents is selected from least one in ethylene carbonate, propene carbonate, gamma-butyrolacton, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate; In described electrolyte, the concentration of lithium salts is 0.5-4.0mol/L, is more preferably 0.8-2.0mol/L.
According to the present invention, under preferable case, also containing film forming agent in described electrolyte, described film forming agent is selected from least one in vinylene carbonate, vinylethylene carbonate, ethylene sulfite, propylene sulfite, Isosorbide-5-Nitrae-sulfonic acid butyrolactone, ethyl sulfate; In described electrolyte, the weight ratio that film forming agent accounts for electrolyte gross weight is 0.1-5%.
Described lithium ion battery can adopt existing method to prepare, such as above-mentioned anode pole piece, barrier film and cathode pole piece are overlapped into battery core successively, load in battery container, inject the electrolyte in battery container, through seal, changing into, partial volume, be standingly made into lithium ion battery.
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Binding agent PVDF is dissolved in solvent NMP (1-METHYLPYRROLIDONE), by positive pole material of lithium cobalt acid LiCoO
2add in this solvent with conductive agent CNT carbon nano-tube, be fully uniformly mixed, obtain anode sizing agent, its composition weight ratio is LiCoO
2: CNT:PVDF=98:1:1.
Be coated on by above-mentioned anode sizing agent on the aluminium foil of 12 μm equably, at 110 DEG C, baking is dry, and roll-in, obtains anode pole piece precursor.Wherein, the thickness of the positive electrode material layer of aluminium foil surface is 100 μm.
Dopamine is dissolved in tris-HCl buffer solution, is mixed with the solution that dopamine concentration is 2g/L, add ammoniacal liquor and regulate pH value to be 8.5, obtain dopamine solution.
Then above-mentioned anode pole piece precursor be impregnated in above-mentioned dopamine solution, take out after 1min, and in vacuum environment, in 70 DEG C of bakings, obtained anode pole piece.Wherein, the thickness of poly-DOPA amine layer is 0.2 μm.
Binding agent CMC (sodium carboxymethylcellulose) is dissolved in water, then adds negative material native graphite, after abundant mix and blend, then add SBR SBR emulsion, continue mix and blend.
Then be coated on equably by this cathode size on the Copper Foil of 10 μm, at 100 DEG C, baking is dry, obtains cathode pole piece after roll-in.Wherein negative pole composition weight ratio is: graphite: CMC:SBR=96.5:1.5:2.
Above-mentioned anode pole piece, cathode pole piece and 16 μm of thick polyethylene porous separator are wound into a square lithium ion battery pole piece, and are accommodated in rectangular cell shell, after baking, inject nonaqueous electrolytic solution (LiPF
6eC/EMC/DEC/VC mixed solution, LiPF
6concentration be 1mol/L, by weight, EC/EMC/DEC=1:1:2, wherein VC is 2% of whole electrolyte weight), sealing, during charging changes into, obtained thickness is 4mm, width 51mm, the rectangular lithium ion battery of height 50mm.
Embodiment 2
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 1, difference is: in dopamine solution, the concentration of dopamine is 20g/L.
Embodiment 3
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 1, difference is: the PH of dopamine solution is 8, and the dip time of anode pole piece precursor in dopamine solution is 10s.
Embodiment 4
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 2, difference is: the dip time of anode pole piece precursor in dopamine solution is 600s.
Embodiment 5
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 2, difference is: the PH of dopamine solution is 7.5, and the dip time of anode pole piece precursor in dopamine solution is 2000s.
Embodiment 6
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 2, difference is: anode pole piece also carries out spray treatment after roll-in.
Embodiment 7
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 3, difference is: anode pole piece also carries out spray treatment after roll-in.
Embodiment 8
The present embodiment is for illustration of anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 4, difference is: anode pole piece also carries out spray treatment after roll-in.
Comparative example 1
This comparative example is used for comparative illustration anode pole piece disclosed by the invention and preparation method thereof, lithium ion battery.
Prepare anode pole piece and lithium ion battery according to the method for embodiment 1, difference is: directly employing does not flood the anode pole piece precursor of dopamine solution as anode pole piece.
Performance test
The lithium ion battery that embodiment 1-8 and comparative example 1 prepare is carried out following performance test:
1, high-temperature storage performance test
Under room temperature condition, lithium ion battery embodiment 1-8 and comparative example 1 prepared to 4.35V, after voltage reaches 4.35V, carries out constant voltage charging respectively at 0.5C current charges, and cut-off current is 0.01C, the charging capacity of record battery.After shelving 5min, the thickness of test battery.Then baking box battery being put into 60 DEG C stores 7 days, takes out afterwards, the thickness of immediate record battery, and then shelve 30min, by battery with 0.2C current discharge to 3.0V, record battery discharge capacity, calculate capability retention and the thickness change of battery.
The test result obtained inserts table 1.
Table 1
| Sample | Capability retention % | Thickness change |
| S1 | 95.3％ | 4.6％ |
| S2 | 94.6％ | 6.2％ |
| S3 | 92.0％ | 5.0％ |
| S4 | 92.9％ | 4.8％ |
| S5 | 88％ | 7.5％ |
| S6 | 93.6％ | 6.0％ |
| S7 | 91.2％ | 5.2％ |
| S8 | 93.2％ | 5.1％ |
| D1 | 78.6％ | 15.4％ |
As can be seen from the test result of table 1, anode pole piece provided by the invention effectively can improve the high-temperature storage performance of lithium ion battery, and at high temperature, the thickness change of lithium ion battery is little.
2, high temperature cyclic performance test
Under temperature is 45 DEG C of conditions, lithium ion battery prepared by embodiment 1 and comparative example 1 all with 0.5C current charges to 4.35V, when voltage reaches 4.35V with constant-potential charge, cut-off current is 0.02C, shelve 5min, then with 0.5C current discharge to 3.0V, shelve 5min.Repeat above step 300 time, by the discharge capacity after lithium ion battery 300 circulations compared with the primary capacity of circulation, calculate capacity surplus ratio.
Its cyclic curve as shown in Figure 1, can obviously be found out from Fig. 1, and anode pole piece provided by the invention effectively can improve the cycle performance of lithium ion battery.
According to above test result, after adopting the inventive method to process positive plate, compared with untreated positive plate, the cycle performance of battery and high-temperature storage performance obtain to be improved significantly.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. an anode pole piece, is characterized in that, comprises plus plate current-collecting body and the positive electrode material layer being attached to described anode collection surface; Described positive electrode material layer surface is also attached with poly-DOPA amine layer.
2. anode pole piece according to claim 1, is characterized in that, the thickness of described poly-DOPA amine layer is 0.005-2 μm.
3. anode pole piece according to claim 1, is characterized in that, described positive electrode material layer comprises positive electrode active materials, and described positive electrode active materials is selected from LiMn
2o
4, LiM
xfe
1-xpO
4, Li
1+al
1-b-cm
bn
co
2in one or more;
Wherein, 0≤x≤1, M be selected from Mn, Ti, Co, V, Mg one or more; 0≤a≤0.2,0≤b≤1,0≤c≤1,0≤b+c≤1.0, L, M, N be in Co, Mn, Ni, Al, Mg, Ga, Sc, Ti, V, Cr, Fe, Cu and Zn one or more.
4. according to the anode pole piece in claim 1-3 described in any one, it is characterized in that, the thickness of described positive electrode material layer is 30-200 μm.
5. as the preparation method of the anode pole piece in claim 1-4 as described in any one, it is characterized in that, comprise the steps:
S1, acquisition anode pole piece precursor; Described anode pole piece precursor comprises plus plate current-collecting body and is attached to the positive electrode material layer of described anode collection surface;
S2, acquisition dopamine solution;
S3, the positive electrode material layer described dopamine solution be arranged on described anode pole piece precursor are surperficial, then dry, form poly-DOPA amine layer, obtain anode pole piece.
6. preparation method according to claim 5, is characterized in that, in described dopamine solution, the concentration of dopamine is 0.1-1000mg/mL.
7. preparation method according to claim 5, is characterized in that, the pH value of described dopamine solution is 7.5-10.
8. according to the preparation method in claim 5-7 described in any one, it is characterized in that, in described step S3, adopt described dopamine solution to flood or positive electrode material layer surface described in spray treatment.
9. preparation method according to claim 8, is characterized in that, when adopting dopamine solution to flood described positive electrode material layer surface, dip time is 1-3600s.
10. according to the preparation method in claim 5-7,9 described in any one, it is characterized in that, in described step S3, the thickness of the poly-DOPA amine layer formed on positive electrode material layer surface is 0.005-2 μm.
11. 1 kinds of lithium ion batteries, is characterized in that, the electrolyte comprising battery container, be arranged at the battery core in battery container and fill in described battery container;
Described battery core comprises the anode pole piece, barrier film and the cathode pole piece that set gradually; Described anode pole piece is the anode pole piece in claim 1-4 described in any one.
12. lithium ion batteries according to claim 11, is characterized in that, described electrolyte comprises electrolyte lithium salt and nonaqueous solvents;
Described lithium salts be selected from lithium perchlorate, lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two trifluoromethanesulfonimide lithium, trifluoromethyl sulfonic acid lithium one or more;
Described nonaqueous solvents is selected from least one in ethylene carbonate, propene carbonate, gamma-butyrolacton, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate;
In described electrolyte, the concentration of lithium salts is 0.5-4.0mol/L.
13. lithium ion batteries according to claim 11 or 12, it is characterized in that, also containing film forming agent in described electrolyte, described film forming agent is selected from least one in vinylene carbonate, vinylethylene carbonate, ethylene sulfite, propylene sulfite, Isosorbide-5-Nitrae-sulfonic acid butyrolactone, ethyl sulfate;
In described electrolyte, the weight ratio that film forming agent accounts for the gross weight of electrolyte is 0.1-5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510494698.1A CN105118958A (en) | 2015-08-13 | 2015-08-13 | Positive electrode plate and preparing method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510494698.1A CN105118958A (en) | 2015-08-13 | 2015-08-13 | Positive electrode plate and preparing method thereof and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105118958A true CN105118958A (en) | 2015-12-02 |
Family
ID=54666892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510494698.1A Pending CN105118958A (en) | 2015-08-13 | 2015-08-13 | Positive electrode plate and preparing method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105118958A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101672750B1 (en) * | 2016-02-11 | 2016-11-04 | 한밭대학교 산학협력단 | Multilayer-structured electrode comprising hydrophilic heat-resistant polymer and manufacturing method for the same, and lithium secondary battery comprising the same |
| CN107394140A (en) * | 2017-07-05 | 2017-11-24 | 河南师范大学 | The preparation method of the sodium iron-based prussian blue electrode material of poly-dopamine cladding |
| WO2018074775A1 (en) * | 2016-10-18 | 2018-04-26 | 주식회사 제낙스 | Metal non-woven fabric electrode having dopamine-based monomer polymerized on surface thereof, and surface modification method therefor |
| CN108232302A (en) * | 2017-12-30 | 2018-06-29 | 国联汽车动力电池研究院有限责任公司 | A kind of high concentration lithium salt electrolyte suitable for silicon-based anode lithium ion battery |
| CN109494345A (en) * | 2018-10-19 | 2019-03-19 | 合肥国轩高科动力能源有限公司 | Battery preparation method for improving safety performance of lithium ion battery and battery |
| CN109698317A (en) * | 2018-12-17 | 2019-04-30 | 广东石油化工学院 | A kind of high-energy density anode composite sheet lithium ion battery |
| CN114142008A (en) * | 2021-11-24 | 2022-03-04 | 蜂巢能源科技有限公司 | Cathode material for relieving oxygen release, preparation method and application |
| CN114883572A (en) * | 2022-03-31 | 2022-08-09 | 蜂巢能源科技股份有限公司 | No negative pole piece and contain its lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101853961A (en) * | 2009-03-31 | 2010-10-06 | 比亚迪股份有限公司 | Method for preparing lithium ion battery |
| US20130302666A1 (en) * | 2012-04-19 | 2013-11-14 | Lg Chem, Ltd. | Electrode active material containing polydopamine and lithium secondary battery including the same |
| CN103545474A (en) * | 2013-10-29 | 2014-01-29 | 中国第一汽车股份有限公司 | Poly-dopamine modified lithium-ion battery diaphragm and preparation method thereof |
| CN104766946A (en) * | 2015-04-13 | 2015-07-08 | 湖南杉杉新能源有限公司 | Lithium ion battery positive pole piece, preparation method of positive pole piece and lithium ion battery |
-
2015
- 2015-08-13 CN CN201510494698.1A patent/CN105118958A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101853961A (en) * | 2009-03-31 | 2010-10-06 | 比亚迪股份有限公司 | Method for preparing lithium ion battery |
| US20130302666A1 (en) * | 2012-04-19 | 2013-11-14 | Lg Chem, Ltd. | Electrode active material containing polydopamine and lithium secondary battery including the same |
| CN103545474A (en) * | 2013-10-29 | 2014-01-29 | 中国第一汽车股份有限公司 | Poly-dopamine modified lithium-ion battery diaphragm and preparation method thereof |
| CN104766946A (en) * | 2015-04-13 | 2015-07-08 | 湖南杉杉新能源有限公司 | Lithium ion battery positive pole piece, preparation method of positive pole piece and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 邓立: "聚多巴胺包覆改性锂离子电池正极材料LiFePO4的研究", 《工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101672750B1 (en) * | 2016-02-11 | 2016-11-04 | 한밭대학교 산학협력단 | Multilayer-structured electrode comprising hydrophilic heat-resistant polymer and manufacturing method for the same, and lithium secondary battery comprising the same |
| WO2018074775A1 (en) * | 2016-10-18 | 2018-04-26 | 주식회사 제낙스 | Metal non-woven fabric electrode having dopamine-based monomer polymerized on surface thereof, and surface modification method therefor |
| CN107394140A (en) * | 2017-07-05 | 2017-11-24 | 河南师范大学 | The preparation method of the sodium iron-based prussian blue electrode material of poly-dopamine cladding |
| CN107394140B (en) * | 2017-07-05 | 2020-05-05 | 河南师范大学 | Preparation method of poly-dopamine-coated sodiumsulverine-based Prussian blue electrode material |
| CN108232302A (en) * | 2017-12-30 | 2018-06-29 | 国联汽车动力电池研究院有限责任公司 | A kind of high concentration lithium salt electrolyte suitable for silicon-based anode lithium ion battery |
| CN109494345A (en) * | 2018-10-19 | 2019-03-19 | 合肥国轩高科动力能源有限公司 | Battery preparation method for improving safety performance of lithium ion battery and battery |
| CN109698317A (en) * | 2018-12-17 | 2019-04-30 | 广东石油化工学院 | A kind of high-energy density anode composite sheet lithium ion battery |
| CN114142008A (en) * | 2021-11-24 | 2022-03-04 | 蜂巢能源科技有限公司 | Cathode material for relieving oxygen release, preparation method and application |
| CN114883572A (en) * | 2022-03-31 | 2022-08-09 | 蜂巢能源科技股份有限公司 | No negative pole piece and contain its lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105206798A (en) | Negative pole piece, preparing method thereof and lithium ion battery | |
| CN110265627B (en) | Positive electrode plate and lithium ion secondary battery | |
| KR102379223B1 (en) | Methods for preparing negative electrode for lithium secondary battery and lithium secondary battery | |
| CN105118958A (en) | Positive electrode plate and preparing method thereof and lithium ion battery | |
| CN101207197B (en) | Lithium ion battery anode material and lithium ion battery and anode containing the material | |
| CN110178252A (en) | The prelithiation method of cathode for secondary cell | |
| US20180233772A1 (en) | Lithium ion secondary battery, and method for producing the same and method for evaluating the same | |
| CN106207087A (en) | A kind of lithium ion battery and preparation method thereof | |
| KR101135605B1 (en) | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same | |
| CN113272995A (en) | Method for producing negative electrode for lithium secondary battery | |
| CN110265626B (en) | Positive pole piece, preparation method thereof and lithium ion secondary battery | |
| JP7237092B2 (en) | Negative electrode for all-solid-state battery and manufacturing method thereof | |
| CN111009650B (en) | Metal lithium surface protection method, negative electrode and metal lithium secondary battery | |
| WO2023070770A1 (en) | Positive plate and lithium-ion secondary battery including same | |
| KR20190083304A (en) | A method of pre-lithiating anode and Anode manufactured therefrom | |
| KR101069100B1 (en) | Lithium secondary battery having a negative electrode including an aqueous binder | |
| CN103855430B (en) | A kind of preparation method of lithium rechargeable battery | |
| CN105932325A (en) | Long-storage life lithium ion storage battery | |
| CN110875491A (en) | Lithium ion secondary battery | |
| CN115136357A (en) | Positive pole piece and lithium ion secondary battery comprising same | |
| KR20190025529A (en) | A method for manufacturing an electrochemical device | |
| JP2019117716A (en) | Secondary battery | |
| CN117219879A (en) | Non-negative electrode lithium ion battery and preparation method thereof | |
| CN103782428A (en) | Lithium ion secondary battery preventing internal short | |
| CN109802176B (en) | Electrolyte and lithium ion battery containing electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151202 |