CN107808978A - A kind of liquid reactive lithium replenishers, Its Preparation Method And Use - Google Patents
A kind of liquid reactive lithium replenishers, Its Preparation Method And Use Download PDFInfo
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- CN107808978A CN107808978A CN201610809466.5A CN201610809466A CN107808978A CN 107808978 A CN107808978 A CN 107808978A CN 201610809466 A CN201610809466 A CN 201610809466A CN 107808978 A CN107808978 A CN 107808978A
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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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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a kind of liquid reactive lithium replenishers for being used to supplement active lithium in lithium ion battery, the liquid reactive lithium replenishers are solution or suspension, include the sulfide and solvent of lithium；Wherein, the solvent can dissolve or partly the sulfide of dissolving lithium and not chemically react between the two；And/or the electrolyte of the solvent and the lithium ion battery does not occur physically and/or chemically to react；And/or the solvent is selected from the electrolyte of the lithium ion battery.Present invention also offers a kind of method that active lithium is supplemented in lithium ion battery and a kind of lithium ion battery.Liquid reactive lithium replenishers provided by the invention are prepared simply, and easy to use, safe, cost is cheap.The various positive electrodes of liquid reactive lithium replenishers and lithium ion battery provided by the invention, negative material and electrolyte compatibility are good, can be used for preparing various lithium ion batteries, so as to improve the reversible charge/discharge capacity of full battery and follow-up cyclical stability.
Description
Technical field
The invention belongs to field of lithium ion battery.In particular it relates to a kind of liquid of sulfide based on lithium is lived
Property lithium replenishers, the invention further relates to the preparation method and its usage of the active lithium replenishers.
Background technology
It is existing because lithium ion battery has the advantages that the cycle life of high discharge voltage, high energy density and length
It is widely used in various small-sized portable electric appts, such as notebook computer, cell phone and video camera, and
Gradually favored by high-tech area, such as space satellite, electric automobile and military affairs, lithium-ion electric is required in these applications
Pond has more preferable capacity and cycle life.
It is known to those skilled in the art that when lithium ion battery carries out first charge-discharge circulation, lithium ion battery
Negative material surface can form a kind of solid electrolyte film (SEI films), while with the cyclic process of lithium ion battery, source
Lithium ion in the lithium ion and electrolyte of the active lithium of positive pole can not be completely out after negative material is embedded into, further
Ground, commercial electrolyte is the carbonic esters such as ethylene carbonate (EC), dimethyl carbonate (DMC), vinylene carbonate (VC) now
Class electrolyte, therefore the main component of SEI films has LiF, Li2CO3With Arrcostab lithium etc., and the lithium ion in these products is main
Active lithium in positive pole, these situations inevitably cause the capacity attenuation and cycle efficieny drop of lithium ion battery
Low, especially after first charge-discharge circulation, cycle efficieny is reduced and become apparent from.
Formed to replenish caused by SEI films and follow-up long circulating irreversible capacity loss during initial charge
The loss of active lithium has reported some supplement lithiums, it is necessary to supplement active lithium in lithium ion battery in existing patent document
Method.
A kind of method that negative pole mends lithium is disclosed in Publication No. CN1290209C Chinese patent, by lithium metal, negative pole
After material and on-aqueous liquid form slurry, scratch on collector, then pole piece is formed through follow-up process.Although this method also may be used
With the active lithium of supplement consumption, but because the activity of lithium metal is very high, easily occur with the oxygen in air, steam and nitrogen
Reaction, therefore whole process needs to carry out under completely anhydrous conditions, process is cumbersome, greatly improves production cost, and lithium
Very big potential safety hazard be present due to easily floating in air in powder.
Proposed in Application No. CN201310070202.9 patent application the lithium replenishers of lithium-containing compound are direct
The surface of positive pole is mixed in positive electrode or is applied directly onto, these lithiums supplement in the charging process of its first charge-discharge circulation
Agent can decompose, there is provided active lithium, although it supplements active lithium to a certain extent, due to the sulfide electronic isolation of lithium
Property, electro-chemical activity is smaller when its particle is larger, first charge-discharge circulation charging when can not completely make activity
Lithium is brought into play, therefore when the sulfide of lithium only being separated into small particle, first charge-discharge circulation is just active, but in advance
The method for preparing the sulfide such as high-energy ball milling of short grained lithium, complex, this will greatly improve cost, and short grained
The sulfide active of lithium is higher, can be reacted quickly with the steam in air rotten, not easy to maintain.
The method that a kind of " wet method benefit lithium " is disclosed in Application No. CN 201210350770.X patent application, will have
Machine lithium sprays or is added dropwise the surface with positive pole, the lithium in organolithium is embedded into after being reduced in positive plate.But the invention is present
Some problems, n-BuLi as used, tert-butyl lithium etc. are high inflammable and explosive dangerous material, and security is unlike lithium powder
It is high；Although the organolithium that being sprayed at the organolithium of positive electrode surface has part is reduced and is embedded in positive pole, also exist a lot
Residual, this can further reduce capacity on the contrary.
Therefore, be currently needed for it is a kind of be used in lithium ion battery supplement active lithium reagent and method, with reduce lithium from
Capacity attenuation of the sub- battery in charge and discharge process, and improve its cycle efficieny.
The content of the invention
In order to make up the deficiencies in the prior art, it is used to supplement active lithium in lithium ion battery the invention provides a kind of
Liquid reactive lithium replenishers.Active lithium replenishers provided by the invention are dissolving or the vulcanization for the lithium being partially dissolved in solvent
Thing, therefore, liquid reactive lithium replenishers provided by the invention can directly prepare the sulfide of short grained lithium and can be with carbon
It is uniform compound, and because the sulfide of the lithium is scattered in a solvent, it is easier to preserve.Present invention also offers the liquid
The application method of active lithium replenishers.Therefore, liquid reactive lithium replenishers preparation method provided by the invention is simple, cost is low and
It may be adapted to volume production, can be widely applied to industrial production.
On the one hand, the invention provides a kind of liquid reactive lithium supplement for being used to supplement active lithium in lithium ion battery
Agent, the liquid reactive lithium replenishers are solution or suspension, include the sulfide and solvent of lithium；
Wherein, the solvent can dissolve or partly dissolve the sulfide of the lithium and not occur between the two chemical anti-
Should；And/or
The electrolyte of the solvent and the lithium ion battery does not occur physically and/or chemically to react；And/or
The solvent is selected from the electrolyte of the lithium ion battery.
Preferably, one or more of the sulfide of the lithium in lithium sulfide, over cure lithium, more lithium sulfides.It is more excellent
Selection of land, the sulfide of the lithium is lithium sulfide.
Preferably, the sulfide of the lithium can with pre-synthesis, or can by by lithium sulfide and sulphur with Li：S is 2：1
~8 mole metering adds solvent as described above than mixing and formed.
Preferably, the molar concentration of lithium ion is 0.01mol/L-5mol/L in the liquid reactive lithium replenishers, more excellent
Selection of land is 0.01mol/L-0.5mol/L, most preferably 0.01mol/L-0.25mol/L.
Preferably, the one or more in the organic solvent of sulfide of the solvent selected from dissolvable lithium；It is highly preferred that
The solvent is selected from the one or more in methanol, ethanol, tetraethyleneglycol dimethyl ether (TEGDME) and dimethyl ether (DME).
Preferably, optional conductive additive and/or optional binding agent are also included in the liquid reactive lithium replenishers；
Preferably, the conductive additive in carbon black conductive agent, conductive charcoal pipe, graphene or graphene oxide one
Kind is a variety of；It is highly preferred that the carbon black conductive agent be selected from acetylene black, Super P, Super S, 350G, carbon fiber (VGCF),
CNT (CNTs), Ketjen black (Ketjen black EC 300J, Ketjen black EC 600JD, Carbon ECP or
Carbon ECP600JD) in one or more；Preferably, in the liquid reactive lithium replenishers conductive additive quality
For the 0~50% of the sulfide quality of the lithium；Preferably 5%~20%；More preferably 5%~10%.Preferably, institute
State binding agent and be selected from polyvinylpyrrolidone (PVP), Kynoar (PVDF), PEO (PEO), polytetrafluoroethylene (PTFE)
(PTFE), the one or more in the copolymer (SBR) of carboxymethyl cellulose (CMC), styrene and butadiene.Preferably, institute
The quality for stating binding agent in liquid reactive lithium replenishers is the 0~20% of the sulfide quality of the lithium；Preferably 2%~
10%；More preferably 2%~5%.
Preferably, the electrolyte is selected from liquid electrolyte, solid electrolyte, semisolid electrolyte and polymer dielectric
In one or more.
On the other hand, the invention provides the preparation method of above-mentioned liquid reactive lithium replenishers, methods described to include following
Step：
The sulfide of lithium, optional conductive additive and optional binding agent are added in solvent and mixed to obtain liquid
Active lithium replenishers.
Preferably, it is described to be added to disposable all additions or substep addition.
On the other hand, the invention provides a kind of method that active lithium is supplemented in lithium ion battery, methods described to include
By above-mentioned liquid reactive lithium replenishers be added in the positive electrode slurry of the lithium ion battery and/or be incorporated into the lithium from
The positive pole of sub- battery and/or it is added in the electrolyte of the lithium ion battery.
Preferably, when the solvent and the active lithium replenishers do not occur physically and/or chemically to react, by the work
Property lithium replenishers add in positive electrode slurry and/or incorporation positive pole；
Preferably, the liquid reactive lithium replenishers are mixed into positive pole using the mode for coating, dipping and/or spraying.It is excellent
Selection of land, the mass percent that the active lithium replenishers account for the positive pole or positive electrode are 0.1-20%, it is therefore preferable to 2%~
10%, more preferably 2~5%.
Preferably, will when the electrolyte of the solvent and the lithium ion battery does not occur physically and/or chemically to react
The liquid reactive lithium replenishers are added in the electrolyte of the lithium ion battery.Preferably, described in being selected from when the solvent
During the electrolyte of lithium ion battery, the liquid reactive lithium replenishers are added in the electrolyte of the lithium ion battery.
Yet another aspect, present invention also offers a kind of lithium ion battery, institute of the present invention is included in the lithium ion battery
The liquid reactive lithium replenishers stated.
On the other hand, present invention also offers a kind of preparation method of lithium ion battery, methods described is including the use of above-mentioned
Liquid reactive lithium replenishers prepare lithium battery to prepare lithium battery, and/or using the above method.
It was found by the inventors of the present invention that active lithium replenishers are added in battery system as a solution, it is first
Obtained sufficient decomposition during charge and discharge cycles, discharge Lithium-ion embeding or be deposited on negative pole or with negative pole alloying, make up negative
Pole forms during SEI films and following cycle the lithium metal being lost and discharges unnecessary active lithium, and negative pole SEI films consume when being formed
Lithium supplemented, therefore, the present inventor dissolved or be partly dissolved using one or more of solvents active lithium supplement
Agent obtains liquid reactive lithium replenishers, is then added into battery system, make lithium ion battery first charge/discharge capacity and
Long circulating stability is obtained for significant raising.Therefore the lithium rechargeable battery of the present invention, can significantly improve energy density
And service life.
Based on this, liquid reactive lithium replenishers provided by the invention are prepared simply, and easy to use, safe, cost is low
It is honest and clean.Further, the various positive electrodes of liquid reactive lithium replenishers and lithium ion battery provided by the invention, negative material and
Electrolyte compatibility is good, can be used for preparing various lithium ion batteries, so as to improve the reversible charge/discharge capacity of full battery and after
Continuous cyclical stability.
Brief description of the drawings
Hereinafter, embodiment of the present invention is described in detail with reference to accompanying drawing, wherein：
The cyclic voltammetric that Fig. 1 is anode pole piece D1 of the present invention and the lithium ion battery (half-cell) of lithium piece composition is bent
Line；
The cyclic voltammetric that Fig. 2 is anode pole piece D3 of the present invention and the lithium ion battery (half-cell) of lithium piece composition is bent
Line；
Fig. 3 is full battery F1 and F3 of the present invention first all charging and discharging curve comparison diagrams；
Fig. 4 is full battery F1 and H1 of the present invention first all charging and discharging curve comparison diagrams；
Embodiment
Further detailed description is carried out to the present invention with reference to embodiment, the embodiment provided is only to illustrate
Invention, the scope being not intended to be limiting of the invention.
Embodiment 1 prepares liquid active lithium replenishers
The present embodiment prepares liquid reactive lithium replenishers according to following step, and the operation is carried out at room temperature：
1. take 0.16g lithium sulfides (Li2S), 0.02g Super P and 0.02g PVP, it is placed in 20ml methanol, surpasses
Sound 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A1.
2. take 0.16g lithium sulfides (Li2S), 0.02g Super P and 0.02g PVP, it is placed in 20ml ethanol, surpasses
Sound 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A2.
3. take 0.16g lithium sulfides (Li2S), 0.02g Super P and 0.02g PVP, it is placed in 20ml TEGDME,
Ultrasonic 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A3.
4. take 0.16g lithium sulfides (Li2S), 0.02g Super P and 0.02g PVP, it is placed in 20ml DME, surpasses
Sound 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A4.
5. take 0.08g lithium sulfides (Li2S), 0.09g Super P and 0.04g PVP, it is placed in 20ml methanol, surpasses
Sound 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A5.
6. take 0.08g lithium sulfides (Li2S), 0.09g Super P and 0.04g PVP, it is placed in 20ml ethanol, surpasses
Sound 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A6.
7. take 0.08g lithium sulfides (Li2S), 0.09g Super P and 0.04g PVP, it is placed in 20ml TEGDME,
Ultrasonic 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A7.
8. take 0.08g lithium sulfides (Li2S), 0.09g Super P and 0.04g PVP, it is placed in 20ml DME, surpasses
Sound 10h, it is stirred for 10h and uniformly mixes, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A8.
9. take 0.18g lithium sulfides (Li2S) and 0.02g PVP, it is placed in 20ml methanol, ultrasonic 10h, is stirred for 10h
Uniformly mixing, produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as A9.
10. take 0.18g lithium sulfides (Li2S) and 0.02g PVP, it is placed in 20ml ethanol, ultrasonic 10h, is stirred for
10h is uniformly mixed, and produces liquid reactive lithium replenishers, and the liquid reactive lithium replenishers are designated as A10.
11. take 0.18g lithium sulfides (Li2S) and 0.02g PVP, it is placed in 20ml TEGDME, ultrasonic 10h, then stir
Mix 10h uniformly to mix, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as A11.
12. take 0.18g lithium sulfides (Li2S) and 0.02g PVP, it is placed in 20ml DME, ultrasonic 10h, is stirred for
10h is uniformly mixed, and produces liquid reactive lithium replenishers, and the liquid reactive lithium replenishers are designated as A12.
13. take 0.18g lithium sulfides (Li2S) and 0.02g Super P, it is placed in 20ml methanol, ultrasonic 10h, then stir
Mix 10h uniformly to mix, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as A13.
14. take 0.18g lithium sulfides (Li2S) and 0.02g Super P, it is placed in 20ml ethanol, ultrasonic 10h, then stir
Mix 10h uniformly to mix, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as A14.
15. take 0.18g lithium sulfides (Li2S) and 0.02g Super P, it is placed in 20ml TEGDME, ultrasonic 10h,
It is stirred for 10h uniformly to mix, produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers is designated as A15.
16. take 0.18g lithium sulfides (Li2S) and 0.02g Super P, it is placed in 20ml DME, ultrasonic 10h, then stir
Mix 10h uniformly to mix, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as A16.
Embodiment 2 prepares liquid active lithium replenishers
The present embodiment prepares liquid reactive lithium replenishers according to following step, and the operation is carried out at room temperature：
1. take 0.0115g lithium sulfides (Li2S) and 0.056g sulphur (S), it is placed on tetraethyleneglycol dimethyl ether (TEGDME)
In, stirring 6h is uniformly mixed, and produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B1.
2. take 0.0115g lithium sulfides (Li2S) and 0.056g sulphur (S), it is placed in dimethyl ether (DME), stirring 6h is uniform
Mixing, produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B2.
3. take 0.0115g lithium sulfides (Li2S) and 0.048g sulphur (S), it is placed on tetraethyleneglycol dimethyl ether (TEGDME)
In, stirring 6h is uniformly mixed, and produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B3.
4. take 0.0115g lithium sulfides (Li2S) and 0.048g sulphur (S), it is placed in dimethyl ether (DME), stirring 6h is uniform
Mixing, produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B4.
5. take 0.0115g lithium sulfides (Li2S) and 0.032g sulphur (S), it is placed on tetraethyleneglycol dimethyl ether (TEGDME)
In, stirring 6h is uniformly mixed, and produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B5.
6. take 0.0115g lithium sulfides (Li2S) and 0.032g sulphur (S), it is placed in dimethyl ether (DME), stirring 6h is uniform
Mixing, produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B6.
7. take 0.0115g lithium sulfides (Li2S) and 0.024g sulphur (S), it is placed on tetraethyleneglycol dimethyl ether (TEGDME)
In, stirring 6h is uniformly mixed, and produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B7.
8. take 0.0115g lithium sulfides (Li2S) and 0.024g sulphur (S), it is placed in dimethyl ether (DME), stirring 6h is uniform
Mixing, produces liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B8.
9. take 0.0115g lithium sulfides (Li2S), it is placed in tetraethyleneglycol dimethyl ether (TEGDME), stirring 6h is uniformly mixed
Close, produce liquid reactive lithium replenishers, the liquid reactive lithium replenishers are designated as B9.
10. take 0.0115g lithium sulfides (Li2S), it is placed in dimethyl ether (DME), stirring 6h is uniformly mixed, and produces liquid
State active lithium replenishers, the liquid reactive lithium replenishers are designated as B10.
The comparative example of embodiment 3
The present embodiment is prepared with active lithium replenishers are compared according to following step, and the operation is carried out at room temperature：
Take 0.16g lithium sulfides (Li2S), 0.02g Super P and 0.02g PVP, are uniformly mixed in NMP, produce activity
Lithium replenishers, the active lithium replenishers are designated as C1.
Take 0.08g lithium sulfides (Li2S), 0.09g Super P and 0.04g PVP, are uniformly mixed in NMP, produce activity
Lithium replenishers, the active lithium replenishers are designated as C2.
Take 0.18g lithium sulfides (Li2S) and 0.02g PVP, uniformly mixed in NMP, produce active lithium replenishers, the work
Property lithium replenishers are designated as C3.
Take 0.18g lithium sulfides (Li2S) and 0.02g Super P, uniformly mixed in NMP, produce active lithium replenishers,
The active lithium replenishers are designated as C4.
The performance test of embodiment 4
1~the A16 of solution A prepared in embodiment 1 is assembled into button cell according to the steps.
The preparation of 4.1 anode pole pieces and cathode pole piece
By LiFePO4As positive electrode active materials, carbon black is as conductive additive, with carboxymethyl cellulose (CMC), benzene second
The copolymer of alkene and butadiene (SBR) is binding agent, is 90 according to mass ratio:7:1:2 are well mixed in water, are prepared into uniformly
Anode sizing agent.Uniform anode sizing agent is coated uniformly in the aluminum foil current collector that thickness is 15 μm, dried at 55 DEG C, shape
Into the pole piece of 100 μ m-thicks, roll-in under roll squeezer (pressure is about 1MPa × 1.5cm2) is placed in, pole piece is cut into a diameter ofDisk, be placed in vacuum drying oven with 120 DEG C of baking 6h, after natural cooling, take out, be placed in glove box and be used as positive pole
Pole piece, it is designated as D1.
Using graphite as negative active core-shell material, carbon black is as conductive additive, with carboxymethyl cellulose (CMC), styrene
Copolymer (SBR) with butadiene is binding agent, is 93 according to mass ratio:2:2:3 are well mixed in water, are prepared into uniform
Cathode size.Uniform cathode size is coated uniformly in the copper foil current collector that thickness is 8 μm, dried at 55 DEG C, formed
50 μm and the pole piece of 59 μ m-thicks, roll-in under roll squeezer (pressure is about 1MPa × 1.5cm2) is placed in, pole piece is cut into a diameter ofDisk, be placed in vacuum drying oven with 120 DEG C of baking 6h, after natural cooling, taking-up, which is placed in glove box, is used as negative pole
Pole piece.
In the glove box full of inert atmosphere, 50 μ lA1~A4,80 μ lA5~A8 and 50 μ l A9~A16 solution are taken
Drop toPositive pole disk on.Dry 10h at 120 DEG C, after natural cooling, as positive pole, be denoted as D2-D17.Take with A1,
The same quality of active lithium replenishers corresponding to A5, A9 and A13 C1~C4 coating withPositive pole disk on.120
Dry 10h at DEG C, after natural cooling, as positive pole, be denoted as E1~E4
4.2 assembling lithium rechargeable batteries
In the glove box full of inert atmosphere, (U.S. Celegard is purchased from using PP/PE/PP trilamellar membrane as barrier film
Company) put between a positive electrode and a negative electrode, 1M LiPF6 are added dropwise and are dissolved in EC/DMC (1：1, volume ratio) (purchase of non-water system electrolyte
From BASF Aktiengesellschaft), 50 μm of the graphite cathode pole piece prepared using in 4.1 is prepared as the negative pole of battery with step 4.1
D1 as positive pole, the button cell for being assembled into model CR2032 is denoted as F1.59 μm of the graphite cathode prepared with step 4.1
Negative pole of the pole piece as battery, using D2-D17 prepared by step 4.1 as positive pole, it is assembled into model CR2032 button cell
It is denoted as F2~F17.Negative pole using 59 μm of graphite cathode pole piece prepared by step 4.1 as battery, the E1 prepared with step 4.1
For~E4 as positive pole, the button cell for being assembled into model CR2032 is denoted as G1~G4.
In the glove box full of inert atmosphere, (U.S. Celegard is purchased from using PP/PE/PP trilamellar membrane as barrier film
Company) put between a positive electrode and a negative electrode, 1M LiPF6 are added dropwise and are dissolved in EC/DMC (1：1, volume ratio) (purchase of non-water system electrolyte
From BASF Aktiengesellschaft), then toward the solution that 30 μ lB1-B10 are added in the electrolyte.59 μm of the graphite 1. prepared with step
Negative pole of the cathode pole piece as battery, using 1. D1 that step is prepared as positive pole, it is assembled into model CR2032 button cell note
It is H1~H10.
After button cell F1~F17, G1~G4 and the H1~H10 of preparation are stood into 24 hours at ambient temperature, adopt
With blue electric 11 battery charging and discharging testers (being purchased from Wuhan Land Electronic Co., Ltd.) to the button cell of above-mentioned preparation
Carry out charge and discharge cycles test.It is 160mAhg that LiFePO4 specific capacity, which is calculated, first-1, with 0.05C circulation 1 week, so
Continued cycling through 100 weeks with 0.2C multiplying power afterwards, wherein, the charging/discharging voltage scope for controlling battery is 2.5V-3.6V.Preparation parameter
And the results detailed in Table one and table two.
As a result
From Fig. 1 cyclic voltammetry curve, it is shown that the redox peaks of LiFePO4, and Fig. 2 this it appears that
There is an oxidation peak in 2.6V or so, it is shown that lithium replenishers start to decompose during first week charging near 2.6V.
Lithium ion battery F1 and F3 first all charging and discharging curve contrasts are shown in Fig. 3, it can be seen that lithium-ion electric
Pond F3 has the capacity of a low potential compared to F1, and the charging capacity in its first week has reached 174.8mAhg-1, this is unnecessary to hold
Amount contribution comes from the decomposition of lithium sulfide, and the discharge capacity in embodiment F3 head weeks is up to 146.6mAhg-1, relative to F1's
Only 131.1mAhg-1 has had more 15.5mAhg-1 capacity, illustrates that lithium sulfide can occur point in initial charge and solve release
Lithium ion, the loss of lithium ion when negative terminal surface forms SEI films is compensate for, compensate the lithium ion damage in positive electrode and electrolyte
Consumption, so as to significantly improve first all reversible discharge capacities of lithium ion battery.
Lithium ion battery F1 and H2 first all charging and discharging curve contrasts are shown in Fig. 4, it can be seen that lithium-ion electric
The capacity that has a low potential of the pond H2 compared to F1, and the charging capacity in its first week has reached 162.1mAhg-1, this is unnecessary
Capacity contribution comes from the decomposition of the sulfide of lithium, and the discharge capacity in H2 head weeks is up to 139mAhg-1, relative to F1 only
131.1mAhg-1 has had more about 10mAhg-1 capacity, illustrates the sulfide of lithium and can occur in initial charge point and explain
Lithium ion is put, the loss of lithium ion when negative terminal surface forms SEI films is compensate for, compensates the lithium ion in positive electrode and electrolyte
Loss, so as to significantly improve first all reversible discharge capacities of lithium ion battery.
100 weeks capability retentions that the lithium ion battery F1~F17 and G1~G4 of different parameters are compared in table one can be with
Find out, the long circulating stability of the battery containing lithium sulfide replenishers has obtained significant raising, illustrates that lithium sulfide decomposes production
The raw active lithium activity that compensate for lithium ion battery and be lost in electrochemistry cyclic process also lasting in follow-up circulation
Lithium.But lithium ion battery G1~G4 capability retention and the capacity in first week are much smaller relative to lithium ion battery F2~F17,
When illustrating the solvent using the sulfide of insoluble lithium, activity is relatively low all to bring into play for it, it is impossible to supplement activity completely
The loss of lithium.
Lithium ion battery F1, H1~H10 of different parameters 100 weeks capability retentions are compared in table two, therefrom can be with
Find out, the reversible capacity and long circulating stability of the lithium ion battery of the replenishers of lithium containing liquid reactive, which are obtained for, greatly to be carried
Height, illustrate caused by lithium sulfide decomposes that active lithium is also lasting in follow-up circulation and compensate for lithium ion battery in electrochemistry
The active lithium being lost in cyclic process.Generally speaking, lithium ion can significantly be improved containing benefit lithium method provided by the invention
The reversible capacity of battery and long cyclical stability.
Table 1 becomes for the lithium ion battery F1~F17 and G1~G4 of different parameters discharge capacity with the change of cycle-index
Gesture
The discharge capacity that table 2 is lithium ion battery F1, H1~H15 of different parameters is with the variation tendency of cycle-index.
Finally it should be noted that：Various embodiments above is merely to illustrate technical scheme, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (9)
1. a kind of liquid reactive lithium replenishers for being used to supplement active lithium in lithium ion battery, the liquid reactive lithium replenishers
For the sulfide and solvent of solution or suspension, including lithium；
Wherein, the solvent can dissolve or partly dissolve the sulfide of the lithium and not chemically react between the two；
And/or
The electrolyte of the solvent and the lithium ion battery does not occur physically and/or chemically to react；And/or
The solvent is selected from the electrolyte of the lithium ion battery.
2. liquid reactive lithium replenishers according to claim 1, wherein, the sulfide of the lithium is selected from lithium sulfide, over cure
Change the one or more in lithium, more lithium sulfides；
Preferably, the sulfide of the lithium is lithium sulfide；
Preferably, the molar concentration of lithium ion is 0.01mol/L-5mol/L in the liquid reactive lithium replenishers, more preferably
For 0.01mol/L-0.5mol/L, most preferably 0.01mol/L-0.25mol/L.
3. liquid reactive lithium replenishers according to claim 1 or 2, wherein, the solvent is selected from the vulcanization that can dissolve lithium
One or more in the organic solvent of thing；Preferably, the solvent is selected from methanol, ethanol, tetraethyleneglycol dimethyl ether and diformazan
One or more in ether.
4. the liquid reactive lithium replenishers according to any one of claim 1-3, wherein, the liquid reactive lithium replenishers
In also include optional conductive additive and/or optional binding agent；
Preferably, one kind in carbon black conductive agent, conductive charcoal pipe, graphene or graphene oxide of the conductive additive or
It is a variety of；It is highly preferred that the carbon black conductive agent is selected from acetylene black, Super P, SuperS, 350G, carbon fiber, CNT, section
One or more during qin is black；Preferably, the quality of conductive additive is the sulphur of the lithium in the liquid reactive lithium replenishers
The 0~50% of compound quality；Preferably 5%~20%；More preferably 5%~10%；Preferably, the binding agent is selected from
Polyvinylpyrrolidone, Kynoar, PEO, polytetrafluoroethylene (PTFE), carboxymethyl cellulose, styrene and butadiene
One or more in copolymer；Preferably, the quality of binding agent is the vulcanization of the lithium in the liquid reactive lithium replenishers
The 0~20% of amount of substance；Preferably 2%~10%；More preferably 2%~5%.
5. the liquid reactive lithium replenishers according to any one of claim 1-4, wherein, the electrolyte is selected from liquid electricity
One or more in Xie Zhi, solid electrolyte, semisolid electrolyte and polymer dielectric.
6. the preparation method of the liquid reactive lithium replenishers according to any one of claim 1-5, methods described include with
Lower step：
The sulfide of lithium, optional conductive additive and optional binding agent are added in solvent and mixed to obtain the liquid
Active lithium replenishers；
Preferably, it is described to be added to disposable all additions or substep addition.
7. a kind of method that active lithium is supplemented in lithium ion battery, methods described are included any one of claim 1-5 institutes
The liquid reactive lithium replenishers stated are added in the positive electrode slurry of the lithium ion battery and/or are incorporated into the lithium ion
The positive pole of battery and/or it is added in the electrolyte of the lithium ion battery.
8. method as claimed in claim 7, wherein, when the solvent and the active lithium replenishers do not occur physics and/or
During chemical reaction, the liquid reactive lithium replenishers are added in positive electrode slurry and/or mixed positive pole；
Preferably, the liquid reactive lithium replenishers are mixed into positive pole using the mode for coating, dipping and/or spraying；
Preferably, the mass percent that the liquid reactive lithium replenishers account for the positive pole or positive electrode is 0.1-20%, excellent
Selection of land is 2%~10%, more preferably 2~5%；
Preferably, when the electrolyte of the solvent and the lithium ion battery does not occur physically and/or chemically to react, by described in
Liquid reactive lithium replenishers are added in the electrolyte of the lithium ion battery；
Preferably, when the solvent is selected from the electrolyte of the lithium ion battery, the liquid reactive lithium replenishers are added
Into the electrolyte of the lithium ion battery.
9. a kind of lithium ion battery, the liquid reactive lithium that the lithium ion battery includes any one of claim 1-5 is mended
Fill agent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610809466.5A CN107808978B (en) | 2016-09-08 | 2016-09-08 | Liquid active lithium supplement, preparation method and application thereof |
| PCT/CN2017/100487 WO2018045940A1 (en) | 2016-09-08 | 2017-09-05 | Liquid active lithium supplement, preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610809466.5A CN107808978B (en) | 2016-09-08 | 2016-09-08 | Liquid active lithium supplement, preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN107808978B CN107808978B (en) | 2020-07-28 |
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| WO2018045940A1 (en) | 2018-03-15 |
| CN107808978B (en) | 2020-07-28 |
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