CN104037418A - Lithium ion battery anode film, preparation and application thereof - Google Patents
Lithium ion battery anode film, preparation and application thereof Download PDFInfo
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- 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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
- H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- 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
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- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention discloses a lithium battery anode film. Specifically, the anode film comprises: (i) a lithium embedded transition metal oxide anode material; (ii) a lithium ion supplement; and (iii) a conductive agent and a binder. The lithium ion supplement in the anode film decomposes during initial charge and releases lithium ions so as to make up lithium ion loss caused by formation of an SEI film on the cathode surface, thereby enhancing the reversible charge-discharge capacity of the lithium ion battery. During preparation of the anode film provided by the invention, the lithium ion supplement can be mixed in the anode material or the conductive agent in advance and also can be used for coating the lithium ion battery anode surface. The lithium ion battery anode film has the advantages of convenient use, low cost, good compatibility with a variety of lithium ion battery systems, and obvious improvement effect on battery electrochemical performance, etc.
Description
Technical field
The invention belongs to lithium ion battery field.Particularly, the present invention relates to a kind of lithium ion cell positive film and preparation and application.
Background technology
Lithium ion battery, since commercialization at the beginning of the eighties in last century, because of features such as it has that voltage is high, specific energy is high, has extended cycle life, non-environmental-pollutions, has been widely used in the portable electric appts such as mobile phone, notebook computer, miniature camera; Lithium ion battery can also replace traditional non-renewable resources such as oil, natural gas; in the fields such as electric tool, electric bicycle, electric automobile, solar cell and wind energy battery energy storage, satellite and space flight, obtain extensive use more, thereby play an important role at aspects such as protection of the environment, the saving irreproducibility energy.
Up to now, the positive electrode of lithium ion mainly contains compound and the modified composites thereof such as cobalt acid lithium, lithium nickelate, lithium nickel cobalt dioxide, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium.Business-like negative material mainly contains native graphite, carbonaceous mesophase spherules, the lithium titanate of surface modification, a small amount of amorphous carbon, hard carbon, Delanium, and carbon silicon materials of studying, silicon materials, nitrogen sill, germanium sill, metal alloy etc.Electrolyte is mainly one or more the mixed solution in the solutes such as the organic solvents such as carbonates, ethers, nitrile and lithium hexafluoro phosphate, LiBF4, lithium perchlorate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium.
In lithium ion battery, can in charge and discharge process, provide Energy Transfer medium Li for lithium ion battery
+only have the solute in positive electrode and electrolyte.Verified at present, at lithium ion battery first charge-discharge circulation time, negative material surface at lithium battery can form a kind of solid electrolyte film (SEI), while is along with the cyclic process of lithium battery, lithium ion in lithium ion and electrolyte is being embedded into after negative material to deviate from completely, both of these case can cause the capacity attenuation of lithium battery and the reduction of cycle efficieny, and cycle efficieny reduces more obvious especially first.
At present conventional additives for battery comprises cathode additive agent, electrolysis additive, three aspects of conductive agent additive, is applied to cathode film formation, the function such as fire-retardant, anti-overcharge.In Chinese patent 201010611339.7, a kind of cathode additive agent is disclosed, wherein cathode additive agent has general formula F (CF2CF2) m (CH2CH2O) nR.Wherein, it is more even that the interpolation of fluorine-containing ether compound can make cathode size mix, and improves electrolyte recoverable amount, improved to a certain extent capacity and the cycle performance of battery, but preparation method's complexity produces noxious substance many.
Therefore, this area, in the urgent need to developing a kind of solution in the charge and discharge cycles process of lithium battery, is reduced its capacity attenuation and is improved method and the product in the lithium ion battery field of its cycle efficieny.
Summary of the invention
Capacity attenuation and cycle efficieny for above-mentioned lithium ion battery reduce this problem, and the object of the invention is to provide a kind of lithium ion cell positive film that contains lithium ion replenishers and corresponding battery.
A first aspect of the present invention, provides a kind of lithium battery anode film, and described cathode film comprises:
(i) embedding lithium transition-metal oxide positive electrode;
(ii) mix lithium ion replenishers among described positive electrode or conductive agent and/or that be coated on lithium ion cell positive surface; And
(iii) conductive agent and binding agent.
In another preference, described embedding lithium transition-metal oxide positive electrode is selected from lower group: cobalt acid lithium, lithium nickelate, lithium nickel cobalt dioxide, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium or its combination.
In another preference, described conductive agent comprises carbon black, graphite, carbon nano-tube, Graphene etc.
In another preference, described binding agent comprises the copolymer (SBR) of Kynoar (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), styrene and butadiene.
In another preference, described cathode film also contains collector aluminium foil.
In another preference, described lithium ion replenishers comprise: lithiated compound, lithium salts, alkyl lithium compounds or its combination.
In another preference, described lithiated compound comprises: lithia, lithium peroxide, super lithia or its combination;
Described alkyl lithium compounds comprises: lithium methoxide, lithium ethoxide, isopropyl lithium alkoxide, ethyl-lithium, isopropyl lithium, butyl lithium or its combination;
Described lithium salts comprises: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, over cure lithium or its combination.
In another preference, described lithium ion replenishers are solid-state or liquid.
In another preference, the mass percent that described lithium ion replenishers account for embedding lithium transition-metal oxide positive electrode is 0.5～10%, is more preferably 1～3%.
A second aspect of the present invention, a kind of method of preparing the lithium battery anode film described in first aspect present invention is provided, described method comprises: a positive electrode slurry (a1) is provided, and described slurry contains embedding lithium transition-metal oxide positive electrode, lithium ion replenishers and conductive agent and binding agent; With described slurry is made to cathode film by applying compressing tablet final vacuum dry mode; Or
Described method comprises: after (a2) lithium ion replenishers and conductive agent being mixed, add embedding lithium transition-metal oxide positive electrode and binding agent, make cathode film by applying the dry mode of compressing tablet final vacuum; Or
Described method comprises: (a3) lithium ion replenishers are coated on to the lithium ion cell positive surface of oven dry, thereby form the lithium battery anode film containing described lithium ion replenishers.
Third aspect present invention, provides a kind of lithium ion battery, comprises the anode film described in first aspect present invention.
In another preference, described lithium ion battery also comprises negative electrode film, barrier film, electrolyte, shell and battery auxiliary system.
In another preference, described electrolyte is liquid electrolyte (electrolyte) or polymer dielectric.
A fourth aspect of the present invention, provides a kind of preparation method of lithium ion cell positive, comprises step: the cathode film described in first aspect present invention is bonded in or is coated on collector, thereby make lithium ion cell positive.
Fifth aspect present invention, provides the application of the lithium battery anode film described in first aspect present invention, for the preparation of lithium battery anode or for the preparation of lithium battery.
Sixth aspect present invention, provides a kind of method that compensates lithium ion battery negative irreversible capacity loss or reduce the loss of lithium ion battery lithium ion, comprises step: add lithium ion replenishers to lithium ion cell positive.
In another preference, described lithium ion replenishers comprise: lithiated compound, lithium salts, alkyl lithium compounds or its combination;
In another preference, described interpolation comprises: lithium ion replenishers are blended among embedding lithium transition-metal oxide positive electrode or conductive agent in advance, also can be coated in lithium ion cell positive surface.
In another preference, described method also comprises that compensation cathode of lithium battery surface forms the lithium ion of the loss of SEI film, thus compensation lithium ion battery negative irreversible capacity loss or the loss of minimizing lithium ion battery lithium ion.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tire out and state no longer one by one at this.
Brief description of the drawings
Fig. 1 is lithium battery 2(half-cell) cyclic voltammetry curve, as can be seen, on the cyclic voltammetry curve of lithium battery 2, find to occur oxidation peak in 4.4V left and right, illustrate that lithium peroxide decomposes at 4.4V, its decomposition has produced lithium ion, can make up the lithium ion loss in positive electrode and electrolyte.
Fig. 2 is contrast lithium battery C2(half-cell) cyclic voltammetry curve, as can be seen, in 4.4V left and right, there is not oxidation peak.
Fig. 3 is the first charge-discharge curve of lithium battery 2, as can be seen, occurs that in 4.4V left and right lithium peroxide decomposes platform, illustrates that lithium peroxide decomposes at 4.4V, and it decomposes the lithium ion producing, and can make up the lithium ion loss in positive electrode and electrolyte.
Fig. 4 is the first charge-discharge curve of contrast lithium battery C2, as can be seen, does not occur that in 4.4V left and right lithium peroxide decomposes platform.
Fig. 5 is lithium battery 3 and the full battery of contrast lithium battery C3() charging and discharging curve, as can be seen, the discharge capacity of lithium battery 3, compared to lithium battery C3, has improved approximately 10%.
Embodiment
The inventor is through extensive and deep research, be surprised to find that first to lithium ion anode and add lithium ion replenishers, can make up the lithium ion loss that negative terminal surface forms SEI film, its catabolite does not affect the performance of lithium ion battery substantially, thereby obviously improve the reversible charge/discharge capacity of lithium ion battery, improved the chemical property of lithium ion battery.Complete on this basis the present invention.
Lithium ion battery
As used herein, term " lithium ion battery " refers to respectively with two secondary cells that reversibly compound of Infix and desfix lithium ion forms as both positive and negative polarity.
In the time that battery charges, lithium ion is deintercalation from positive pole, in negative pole, embed, otherwise when electric discharge.The positive pole of lithium ion battery before assembling in embedding lithium state.Conventionally, select the embedding lithium transition-metal oxide of good stability to do positive electrode.
In the present invention, material as negative pole is not particularly limited, can be the various different materials that current potential approaches lithium current potential and can embed lithium compound, representative example comprises (but being not limited to): native graphite, synthetic graphite, carbon fiber, mesophase ball carbon element etc. and metal oxide, comprise SnO, SnO
2, tin composite oxides etc.
In the present invention, electrolyte is not particularly limited, and can be liquid electrolyte (electrolyte) or polymer dielectric.Representational example comprises (but being not limited to): adopt LiPF
6the mixed solvent system of the alkyl carbonic ether such as ethene carbonic ether (EC), propylene carbonate (PC) and low viscosity diethyl carbonic ether (DEC) collocation.
Lithium ion replenishers
As used herein, term " lithium ion replenishers ", " lithium ion additive " can be replaced use, all refer to be applied to the lithium battery additive for supplementary lithium ion of lithium battery anode.
Can be used for lithium ion replenishers of the present invention and be not particularly limited, can be the oxidation Decomposition current potential of any decomposition electric potential lower than electrolyte, and higher than the lithium ion replenishers of the electric discharge stopping potential of anode.
Provide Li can decompose
+as containing in lithium material of lithium ion replenishers, what lithium ion content was the highest is lithium simple substance.And lithium simple substance stability is higher relatively, preferred lithium ion replenishers are oxidation state lithium ion compound.
The decomposition electric potential that can be used for lithium ion replenishers of the present invention should be lower than the oxidation Decomposition current potential of electrolyte, and higher than the electric discharge stopping potential of anode.
Conventional lithium ion replenishers are selected from:
Contain lithium mineral-type: lithia, lithium peroxide, super lithia, lithium hydride, lithium fluoride, lithium nitride, lithium sulfide, aluminium lithium alloy;
Containing lithium organic: lithium methoxide, lithium ethoxide, isopropyl lithium alkoxide, ethyl-lithium, isopropyl lithium, butyl lithium, hexahydroxybenzene lithium.
Can be used for lithium ion replenishers of the present invention is preferably: lithium peroxide, super lithia, lithium nitride, lithium sulfide, aluminium lithium alloy, lithium methoxide, lithium ethoxide, isopropyl lithium alkoxide, ethyl-lithium, isopropyl lithium, butyl lithium;
More preferably, be lithium peroxide, super lithia, lithium nitride.
By lithium ion replenishers being blended among positive electrode or conductive agent in advance or being coated in means such as drying anodal surface, by wherein one or more make an addition to lithium ion cell positive.In lithium battery initial charge process, lithium ion replenishers can decompose, discharge lithium ion, can make up the lithium ion loss that negative terminal surface forms SEI film, lithium ion loss in compensation positive electrode and electrolyte, other catabolites do not affect the performance of lithium ion battery substantially simultaneously, thereby obviously improve the reversible charge/discharge capacity of lithium ion battery, have improved the chemical property of lithium ion battery.And the present invention's lithium ion replenishers used chemical state is stable, in air, be difficult for decomposing, low to technological process and environmental requirement, production cost is low.
Lithium battery anode film and preparation thereof
Lithium battery anode film
A kind of lithium battery anode film provided by the invention, comprising:
(i) embedding lithium transition-metal oxide positive electrode;
(ii) mix lithium ion replenishers among described positive electrode or conductive agent and/or that be coated on lithium ion cell positive surface; And
(iii) conductive agent and binding agent.
Wherein said embedding lithium transition-metal oxide positive electrode is selected from lower group: cobalt acid lithium, lithium nickelate, lithium nickel cobalt dioxide, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium or its combination.
Described lithium ion replenishers comprise: lithiated compound, lithium salts, alkyl lithium compounds or its combination;
Wherein, described lithiated compound comprises: lithia, lithium peroxide, super lithia or its combination;
Described alkyl lithium compounds comprises: lithium methoxide, lithium ethoxide, isopropyl lithium alkoxide, ethyl-lithium, isopropyl lithium, butyl lithium or its combination;
Described lithium salts comprises: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, over cure lithium or its combination.
Described lithium ion replenishers are solid-state.
Described conductive agent comprises carbon black, graphite, carbon nano-tube, Graphene etc.
Described binding agent comprises PVDF, PTFE, CMC, SBR etc., and wherein PVDF is Kynoar, and PTFE is polytetrafluoroethylene, and CMC is carboxymethyl cellulose, and SBR is the copolymer (butadiene-styrene rubber) of styrene and butadiene.
Described cathode film also contains collector aluminium foil.
The mass percent that described lithium ion replenishers account for embedding lithium transition-metal oxide positive electrode is 0.5～10%, is more preferably 1～3%.
Lithium ion replenishers provided by the invention, described replenishers can be blended in advance in positive electrode or conductive agent and use, and the lithium ion cell positive surface that also can be coated in oven dry is used.
Preparation
The method of preparing lithium battery anode film of the present invention can be sneaked into lithium ion replenishers in anode material of lithium battery or slurry and/or after conventional lithium battery anode preparation and is coated on anode.Particularly, preparation method used comprises following three kinds conventionally:
(a1) provide a positive electrode slurry, described slurry contains embedding lithium transition-metal oxide positive electrode, lithium ion replenishers and conductive agent and binding agent; With described slurry is made to cathode film by applying compressing tablet final vacuum dry mode; Or
(a2) lithium ion replenishers and conductive agent are shifted to an earlier date to ball milling and add embedding lithium transition-metal oxide positive electrode and binding agent after mixing, also make cathode film by applying the dry mode of compressing tablet final vacuum; Or
(a3) lithium ion replenishers are coated on to the lithium ion cell positive surface of oven dry, thereby form the lithium battery anode film containing described lithium ion replenishers.
Anode
Anode of the present invention contains lithium ion replenishers of the present invention;
Anode of the present invention also contains conductive agent and binding agent, and wherein said conductive agent is carbon black, graphite, carbon nano-tube, Graphene etc.; Described binding agent is PVDF, PTFE, CMC, SBR etc.; Collector is aluminium foil.
Preferred preparation method comprises step:
Positive electrode is evenly mixed in solution (as nitrogen methyl pyrrolidone (NMP)) with lithium ion replenishers, conductive agent, binding agent respectively, regulate suitable lithium ion replenishers and the mass ratio of positive electrode, and the mass ratio of positive electrode, acetylene black and binding agent, then apply compressing tablet on aluminium foil, make positive pole; Or
Cathode film of the present invention is bonded in to collector, thereby makes lithium ion cell positive.
Conventionally the mass percent that, a kind of suitable lithium ion replenishers account for positive electrode is 0.5～10%.
Beneficial effect of the present invention:
1. improve the reversible charge/discharge capacity of lithium battery: in lithium battery anode film of the present invention, added lithium ion replenishers, can in lithium battery initial charge process, there is to decompose release lithium ion, can make up the lithium ion loss that negative terminal surface forms SEI film, lithium ion loss in compensation positive electrode and electrolyte, other catabolites do not affect the performance of lithium ion battery substantially simultaneously, thereby obviously improve the reversible charge/discharge capacity of lithium ion battery, improved the chemical property of lithium ion battery.
2. lithium ion replenishers chemical state is stable, cathode film preparation cost is low: the inorganic or organic compound containing lithium that the present invention's lithium ion replenishers used are oxidation state, more stable compared with reduction-state additive in conventional art, low to battery preparation flow and process environments requirement, thus reduce preparation cost.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, the condition of conventionally advising according to normal condition or according to manufacturer.
The preparation of embodiment 1 anode 1
Commercial Li-ion battery LiFePO 4 of anode material is evenly mixed in nitrogen methyl pyrrolidone (NMP) solution with lithium ion replenishers lithium peroxide, conductive agent acetylene black and binding agent Kynoar (PVDF) respectively.
The quality of adding lithium peroxide is 1% of LiFePO 4 of anode material quality, and the mass ratio of positive electrode, acetylene black and binding agent is respectively 85:10:5, then applies compressing tablet on aluminium foil, makes anode 1.
Embodiment 2 lithium battery 2(half-cells) preparation
By anode 1, taking metal lithium sheet as anodal, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and the solution of dimethyl carbonate are as electrolyte, and the polyethylene of 20 micron thick is barrier film, is assembled into CR2032 type lithium coin cells 2.
The full battery of embodiment 3 lithium battery 3() preparation
By anode 1, taking graphite as negative pole, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and the solution of dimethyl carbonate are as electrolyte, and the polyethylene of 20 micron thick is barrier film, is assembled into 18650 type cylindrical lithium batteries 3.
The preparation of the anodal C1 of comparative example 1 control cell
Commercial Li-ion battery LiFePO 4 of anode material is evenly mixed in nitrogen methyl pyrrolidone (NMP) solution with conductive agent acetylene black, binding agent Kynoar (PVDF) respectively, the mass ratio of positive electrode, acetylene black and binding agent is respectively 85:10:5, then apply compressing tablet on aluminium foil, make the anodal C1 of control cell.
Comparative example 2 contrasts lithium battery C2(half-cell) preparation
Preparation method is with embodiment 2, and different is to replace anode 1 with the anodal C1 of control cell.
Be assembled into CR2032 type lithium coin cells C2.
Comparative example 3 contrasts the full battery of lithium battery C3() preparation
Preparation method is with embodiment 3, and different is to replace anode 1 with the anodal C1 of control cell.
Be assembled into 18650 type lithium battery C3.
Embodiment 4 lithium battery 2(half-cells) and contrast lithium battery C2(half-cell) chemical property
In the present embodiment, by conventional method, adopt commercially available equipment to carry out electrochemical property test, method of testing is as follows:
A respectively on electrochemical workstation, in 2.0-4.75V voltage range, scans battery cathode with 0.01mV/s speed from anode by lithium battery 2 and contrast lithium battery C2;
Lithium battery 2 and contrast lithium battery C2 on charging-discharge tester system, are carried out respectively charge-discharge test by B, in 2.0-4.4V voltage range, battery charging and discharging tested with the constant current of 5mA/g.
The full battery of embodiment 5 lithium battery 3() and contrast lithium battery C3(full battery) chemical property
18650 type lithium batteries 3 and contrast lithium battery C3 are carried out to charge-discharge test on charging-discharge tester system.In 2.4-4.4V voltage range, battery is carried out to charge-discharge test with the constant current of 5mA/g.
Result:
Lithium battery 2 and contrast lithium battery C2(half-cell) test result as shown in Fig. 1,2,3 and 4, lithium battery 3 and the full battery of contrast lithium battery C3() test result as shown in Figure 5:
(1) as shown in Figure 1, after having added specific lithium ion replenishers, in the cyclic voltammetry curve of lithium battery 1, presented the decomposition peak of lithium ion replenishers, thereby there is decomposition at 4.4V in explanation lithium peroxide.
On the cyclic voltammetry curve of contrast lithium battery C2, not there is oxidation peak (seeing Fig. 2) in 4.4V left and right, illustrate that not having lithium ion to decompose produces; Result shows: the lithium ion replenishers lithium peroxide of interpolation can decompose generation lithium ion, can make up the lithium ion loss in positive electrode and electrolyte.
(2), on the first charge-discharge curve of lithium battery 2, find to occur that in 4.4V left and right lithium peroxide decomposes platform.(seeing Fig. 3); On the first charge-discharge curve of contrast lithium battery C2, do not find that lithium peroxide decomposes platform (seeing Fig. 4); Result shows: lithium peroxide decomposes at 4.4V, and it decomposes the lithium ion producing, and can make up the lithium ion loss in positive electrode and electrolyte.
(3) relatively 18650 type lithium batteries 3 and the full battery of contrast lithium battery C3() charging and discharging curve (see figure 5), discovery has been added after lithium ion replenishers, the discharge capacity of lithium battery 3 is 1426mAh, has improved approximately 10% compared to the contrast lithium battery C3 that does not add lithium ion replenishers.Result shows, in the time of initial charge, can there is to decompose release lithium ion in lithium ion replenishers, can make up the lithium ion loss that negative terminal surface forms SEI film, the lithium ion in compensation positive electrode and electrolyte loses, thereby obviously improves the reversible charge/discharge capacity of lithium ion battery.
Embodiment 6
Prepare lithium battery (full battery) 4,5,6 according to the method for embodiment 1-3, do not contain lithium battery (full battery) C4, C5, the C6 of lithium ion replenishers according to the method preparation of comparative example 1-3, and carry out charge/discharge capacity test according to embodiment 5.Preparation parameter and test result are asked for an interview table 1.
Table 1
From table 1, after having added lithium ion replenishers to lithium battery anode, the lithium battery that the charge/discharge capacity of all batteries does not all add lithium ion replenishers has increased more than 10%.
All documents of mentioning in the present invention are all quoted as a reference in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a lithium battery anode film, is characterized in that, described cathode film comprises:
(i) embedding lithium transition-metal oxide positive electrode;
(ii) mix lithium ion replenishers among described positive electrode or conductive agent and/or that be coated on lithium ion cell positive surface; And
(iii) conductive agent and binding agent.
2. lithium battery anode film as claimed in claim 1, is characterized in that, described lithium ion replenishers comprise: lithiated compound, lithium salts, alkyl lithium compounds or its combination.
3. lithium ion replenishers as claimed in claim 2, is characterized in that,
Described lithiated compound comprises: lithia, lithium peroxide, super lithia or its combination;
Described alkyl lithium compounds comprises: lithium methoxide, lithium ethoxide, isopropyl lithium alkoxide, ethyl-lithium, isopropyl lithium, butyl lithium or its combination;
Described lithium salts comprises: lithium carbonate, lithium borohydride, lithium fluoride, lithium nitride, lithium sulfide, over cure lithium or its combination.
4. lithium battery anode film as claimed in claim 1, is characterized in that, the mass percent that described lithium ion replenishers account for embedding lithium transition-metal oxide positive electrode is 0.5～10%, is more preferably 1～3%.
5. a method of preparing lithium battery anode film as claimed in claim 1, is characterized in that,
Described method comprises: a positive electrode slurry (a1) is provided, and described slurry contains embedding lithium transition-metal oxide positive electrode, lithium ion replenishers and conductive agent and binding agent; With described slurry is made to cathode film by applying compressing tablet final vacuum dry mode; Or
Described method comprises: after (a2) lithium ion replenishers and conductive agent being mixed, add embedding lithium transition-metal oxide positive electrode and binding agent, make cathode film by applying the dry mode of compressing tablet final vacuum; Or
Described method comprises: (a3) lithium ion replenishers are coated on to the lithium ion cell positive surface of oven dry, thereby form the lithium battery anode film containing described lithium ion replenishers.
6. a lithium ion battery, is characterized in that, comprises anode film as claimed in claim 1.
7. a preparation method for lithium ion cell positive, is characterized in that, comprises step: cathode film claimed in claim 1 is bonded in or is coated on collector, thereby make lithium ion cell positive.
8. an application for lithium battery anode film claimed in claim 1, is characterized in that, for the preparation of lithium battery anode or for the preparation of lithium battery.
9. a method that compensates lithium ion battery negative irreversible capacity loss or the loss of minimizing lithium ion battery lithium ion, is characterized in that, comprises step: add lithium ion replenishers to lithium ion cell positive.
10. method as claimed in claim 9, it is characterized in that, described method also comprises that compensation cathode of lithium battery surface forms the lithium ion of the loss of solid electrolyte film (SEI film), thus compensation lithium ion battery negative irreversible capacity loss or the loss of minimizing lithium ion battery lithium ion.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310070202.9A CN104037418A (en) | 2013-03-05 | 2013-03-05 | Lithium ion battery anode film, preparation and application thereof |
| CN201910036599.7A CN109659496A (en) | 2013-03-05 | 2013-03-05 | A kind of lithium ion cell positive film and its preparation and application |
| PCT/CN2013/091128 WO2014134967A1 (en) | 2013-03-05 | 2013-12-31 | Positive electrode film of lithium ion battery and preparation and application therefor |
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| WO2014134967A1 (en) | 2014-09-12 |
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