CN109686923A - The preparation method of pre- embedding cathode of lithium and pre- embedding cathode of lithium, energy storage device, energy-storage system and the electrical equipment being prepared - Google Patents
The preparation method of pre- embedding cathode of lithium and pre- embedding cathode of lithium, energy storage device, energy-storage system and the electrical equipment being prepared Download PDFInfo
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Abstract
The present invention relates to new energy fields, specifically, the pre- embedding cathode of lithium, energy storage device, energy-storage system and the electrical equipment that provide a kind of preparation method of pre- embedding cathode of lithium and be prepared.The preparation method of the pre- embedding cathode of lithium, including a half-cell is provided, charge or discharge are carried out to the half-cell；Wherein, the working electrode of half-cell is metal material, is the material for being capable of providing lithium source to electrode, and electrolyte is the lithium salt solution containing additive；The metal material includes metal, alloy or the metallic composite that alloying reaction can occur with lithium ion；The additive includes that can decompose and form the substance of SEI film in the metal material surface.It is this method simple process, low in cost, this method can form SEI passivating film in metal material surface, avoid cathode from generating volume expansion and by dusting, to improve the stability of cathode, and the alloy that pre- embedding lithium is formed helps to improve coulombic efficiency, to improve discharge capacity and cycle performance.
Description
Technical field
The present invention relates to new energy fields, a kind of preparation method in particular to pre- embedding cathode of lithium and are prepared
Pre- embedding cathode of lithium, energy storage device, energy-storage system and electrical equipment.
Background technique
As green energy storage device, using lithium ion battery as the secondary cell of representative by between electric energy and chemical energy can
Reversal realizes storage and electric discharge, is widely used in every field.Lithium ion battery is mainly by positive and negative anodes active material, afflux
Body, the electrolysis major parts such as pendular ring and diaphragm composition.Lithium ion battery moves back and forth between positive electrode and negative electrode by lithium ion
(insertion and deintercalation process) realizes the charge and discharge process (therefore being also known as " rocking chair type battery ") of battery, specifically, charging
When, lithium ion is deviate from from anode, is embedded in cathode by electrolyte；Discharge process is then opposite.Due to by positive and negative pole material theory
The energy density of the limitation of specific capacity, commercial li-ion battery is extremely limited.Wherein, negative electrode material is at present mainly using modified day
Right graphite, artificial graphite etc., however, the specific capacity of graphite electrode limited (372mAh/g) and having nearly reached the limit；
Graphite cathode compacted density is lower simultaneously, significantly limits the acquisition of the high volume energy density of battery.Therefore, for more honest and cleaner
Valence, efficient and inexpensive negative electrode material key technology research and development seem especially urgent.
Preliminary studies have shown that using high capacity, low cost cheap metal foil as battery cathode, using metal and lithium from
The alloying of son/removal alloying process realizes the discharge and recharge reaction of battery, can obtain the new of height ratio capacity and high-energy density
Type lithium ion battery.Compared to conventional commercial graphite negative electrodes, metal negative electrode has clearly in terms of improving battery capacity
Advantage.By taking metallic aluminium as an example, theoretical specific capacity is up to 993mAh/g (alloying forms LiAl), about graphite cathode capacity
3 times.In addition, cheap metal aluminium has excellent electric conductivity, the negative electrode active material and cathode collection of battery can be functioned simultaneously as
Fluid reduces production cost, while increasing the energy density of lithium ion battery to be conducive to reduce battery volume weight.In
Shenzhen Xianjin Technology Academe, the academy of sciences, state once utilized the height ratio capacity and good conductive characteristic of metallic aluminium, same with metal aluminum foil
Shi Zuowei negative electrode active material and collector, traditional cobalt acid lithium, LiFePO4, ternary material are positive electrode active materials, are set up
Novel battery system, and applied for relevant patent (CN106654289A；PCT/CN2016/081346).This system can
The energy density of lithium ion battery is greatly improved, the overall cost of battery is significantly reduced, therefore with before good commercialization
Scape；However metal aluminum foil, during alloying/removal alloying occurs, volume can expand, and cause dusting, lead to battery
Coulombic efficiency is not high, and capacity attenuation is fast.
In order to make full use of cheap, capacity height and the simple metal foil of preparation process as battery cathode, solve simultaneously
The problem of coulombic efficiency that metal foil is generated as battery cathode is low and easy dusting, the method generallyd use is to foil
Material carries out porous design or carries out surface cladding to it.For example, patent PCT/CN2016/081344 and PCT/CN2016/
It proposes in 081345, by carrying out porous design to metal aluminum foil, while using the means of material with carbon-coated surface, can effectively press down
Dusting of the aluminum honeycomb processed in charge and discharge process improves the service life cycle and charge-discharge magnification performance of battery.On however,
The method stated needs to use more complicated process means, for example laser beam perforation, electrochemical corrosion, high temperature cabonization etc., to increase
The overall cost of battery is added.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of pre- embedding cathode of lithium, this method simple process, cost
Cheap, this method can form SEI passivating film in metal material surface, and cathode is avoided to generate volume expansion and by dusting, thus
The stability of cathode is improved, and the alloy that pre- embedding lithium is formed helps to improve coulombic efficiency, to improve discharge capacity and circulation
Performance.
The second object of the present invention be to provide a kind of preparation method using above-mentioned pre- embedding cathode of lithium be prepared it is pre-
Embedding cathode of lithium, the cathode have low in cost, stability is high, self weight is low, energy density is high, specific capacity is high, coulomb effect height and
The advantages of good cycle.
The third object of the present invention is to provide a kind of energy storage device, which includes using above-mentioned pre- embedding cathode of lithium
The pre- embedding cathode of lithium that is prepared of preparation method, have that cheap device cost, stable structure, coulombic efficiency be high, discharge capacity
The advantages of high, energy density height and good cycle.
The fourth object of the present invention is to provide a kind of energy-storage system, which includes above-mentioned energy storage device, is had
The advantages of low in cost, stable structure, coulombic efficiency are high, specific capacity is high, energy density is high and good cycle.
The fifth object of the present invention is to provide a kind of electrical equipment, which includes above-mentioned energy storage device, is had
Low in cost, the advantages of specific capacity is high, energy density is high and good cycle, the electrical equipment identical charging and discharging currents with
And in use, the service life is longer under identical environment.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
In a first aspect, a half-cell is provided the present invention provides a kind of preparation method of pre- embedding cathode of lithium, to half electricity
Pond carries out charge or discharge；
Wherein, the working electrode of the half-cell is metal material, is the material for being capable of providing lithium source, electrolyte to electrode
For the lithium salt solution containing additive；
The metal material includes metal, alloy or the metallic composite that alloying reaction can occur with lithium ion；
The additive includes that can decompose and form the substance of SEI film in the metal material surface.
As further preferably technical solution, the metal is aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth
In any one；
Or, the alloy is including at least any one in aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth
Alloy；
Or, the metallic composite is including at least appointing in aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth
The composite material of one kind of anticipating；
Preferably, the metal material with a thickness of 10-1000 μm.
As further preferably technical solution, the material for being capable of providing lithium source includes the chemical combination of lithium metal or lithium
Object；
Preferably, the compound of the lithium includes lithium sulfide, lithia, lithium selenide, lithium fluoride, lithium oxalate, cobalt acid lithium, carbon
At least one of sour lithium or LiFePO4；
Preferably, described is lithium metal to electrode, is discharged using lithium metal as the half-cell to electrode；
Preferably, described is the compound of lithium to electrode, is filled to using the compound of lithium as the half-cell to electrode
Electricity.
As further preferably technical solution, the additive includes LiBOB, LiODFB, LiPO2F2、LiDFOP、
At least one of LiBMB, LiDFMFMB, LiDFEFMB, LiDFPFMB or LiTFOP；
Preferably, the mass fraction of the additive in the electrolytic solution is 0.1%-30%, preferably 8%-15%；
Preferably, the lithium salts in electrolyte include lithium hexafluoro phosphate, LiBF4, lithium chloride, lithium carbonate, lithium sulfate,
Lithium nitrate, lithium fluoride, trifluoromethanesulfonic acid lithium, bis- (trifluoromethyl sulfonyl) imine lithiums, double fluorine sulfimide lithiums or lithium perchlorate
At least one of；
Preferably, in the electrolyte, the concentration of lithium salts is 0.1-10mol/L；
Preferably, the solvent of the electrolyte includes at least one of esters, sulfone class, ethers, nitrile or olefines；
Preferably, the solvent of the electrolyte includes propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate
(DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), N, N- dimethyl second
Amide (DMA), fluorinated ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), γ-Ding Nei
Ester (GBL), tetrahydrofuran (THF), 2- methyltetrahydrofuran (2MeTHF), 1,3- dioxolanes (DOL), 4- methyl-1,3-
Dioxolanes (4MeDOL), dimethoxymethane (DMM), 1,2- diformazan Ethylene Oxide (DMP), triethylene glycol dimethyl ether (DG), two
Methyl sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), sulfurous acid propylene rouge (PS), two formicester of sulfurous acid (DMS),
At least one of sulfurous acid diethyl rouge (DES) or crown ether (12-crown-4).
As further preferably technical solution, the electric current of charge or discharge is 0.01-1mA/cm2, charge or discharge
Time is 100-1 hours；
Preferably, the half-cell further includes diaphragm, the diaphragm include glass fibre, polyethylene diagrams, polypropylene every
At least one of film or polypropylene, polyethylene/polypropylene diaphragm.
Second aspect, the present invention provides a kind of pre- embedding lithiums that the preparation method using above-mentioned pre- embedding cathode of lithium is prepared
Cathode.
The third aspect, the present invention provides a kind of energy storage devices, including the preparation method system using above-mentioned pre- embedding cathode of lithium
Pre- embedding cathode of lithium made of standby.
As further preferably technical solution, the energy storage device further includes positive electrode；
Preferably, energy storage device is lithium ion battery, and positive electrode includes LiMn2O4, cobalt acid lithium, LiFePO4 or ternary
At least one of material；
Preferably, energy storage device is lithium-ion capacitor, positive electrode include active carbon, carbon nanotube, activated carbon fiber,
At least one of graphene, mesoporous carbon, carbon molecular sieve or carbon foams；
Preferably, energy storage device is Dual-ion cell, and positive electrode includes natural graphite and/or expanded graphite.
Fourth aspect, the present invention provides a kind of energy-storage systems, including above-mentioned energy storage device.
5th aspect, the present invention provides a kind of electrical equipments, including above-mentioned energy storage device.
Compared with prior art, the invention has the benefit that
It uses metal material as working electrode in the preparation method of pre- embedding cathode of lithium provided by the present invention, be capable of providing
The material of lithium source charges as the half-cell assembled to electrode and the lithium salt solution for containing additive as electrolyte
Or electric discharge.The working mechanism of above-mentioned pre- embedding lithium are as follows: during charge or discharge, the additive in electrolyte divides first
Solution, to form SEI passivating film in metal material surface, during further progress charge or discharge, lithium ion passes through blunt
Change film and alloying reaction occurs for metal material, the alloy of metal material and lithium is formed, to complete the process of pre- embedding lithium.To electricity
Pole is primarily to provide the lithium source of pre- embedding lithium；It is that pre- embedding lithium is negative after the completion of pre- embedding lithium using the working electrode of metal material
Pole.
It is above method simple process, low in cost.The SEI passivating film formed in above-mentioned pre- process of intercalation is conducive to improve negative
The stability of pole reduces the volume expansion that cathode generates during alloying/removal alloying occurs with lithium ion, avoids
Cathode is by dusting, and the alloy that pre- embedding lithium is formed helps to improve coulombic efficiency, improves discharge capacity and cycle performance.In addition,
Due to the metal material that cathode is pre- embedding lithium, metal material is used as negative electrode active material and negative current collector simultaneously, can be effective
The self weight for mitigating cathode, further increases the energy density and specific capacity of energy storage device.
Cost is relatively low for the pre- embedding cathode of lithium obtained using the preparation method of above-mentioned pre- embedding cathode of lithium, and stabilization with higher
Property, the volume expansion generated during alloying/removal alloying occurs with lithium ion is small, is not easy by dusting, coulomb
Effect is high, good cycle, and the cathode has the advantages that self weight is low, can further increase the energy density of energy storage device with
Specific capacity.
Energy storage device provided by the invention includes the pre- embedding lithium being prepared using the preparation method of above-mentioned pre- embedding cathode of lithium
Cathode, thus there is high cheap device cost, stable structure, coulombic efficiency, discharge capacity height, energy density height and cycle performance
Good advantage.
Energy-storage system provided by the invention includes above-mentioned energy storage device, thus is at least had identical with above-mentioned energy storage device
Advantage has the advantages that low in cost, stable structure, coulombic efficiency are high, specific capacity is high, energy density is high and good cycle.
Electrical equipment provided by the invention includes above-mentioned energy storage device, thus is at least had identical with above-mentioned energy storage device
Advantage has the advantages that low in cost, specific capacity is high, energy density is high and good cycle, which fills identical
In use, the service life is longer under discharge current and identical environment.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of half-cell in the preparation method of the pre- embedding cathode of lithium of one embodiment of the present invention；
Fig. 2 is the structural schematic diagram of the energy storage device of one embodiment of the present invention；
Fig. 3 is embodiment 1 and the pre- embedding lithium discharge curve of comparative example 1；
Fig. 4 (a) is the surface topography for the pre- embedding cathode of lithium that comparative example 1 obtains；
Fig. 4 (b) is the surface topography for the pre- embedding cathode of lithium that embodiment 1 obtains.
Icon: 1- working electrode；2- is to electrode；3- half-cell electrolytes；5- half-cell diaphragm；The pre- embedding cathode of lithium of 6-；7-
Energy storage device electrolyte；9- energy storage device diaphragm；10- positive active material；11- plus plate current-collecting body.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.
It should be understood that
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation method
It can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating
Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating
The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a-b " indicates the breviary of any real combinings between a to b
It indicates, wherein a and b is real number.Such as numberical range " 0.01-1 " indicate herein all listed " 0.01-1 " it
Between whole real numbers, " 0.01-1 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into
Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
In a first aspect, providing a kind of preparation method of pre- embedding cathode of lithium at least one embodiment, half electricity is provided
Pond carries out charge or discharge to the half-cell；
Wherein, the working electrode of the half-cell is metal material, is the material for being capable of providing lithium source, electrolyte to electrode
For the lithium salt solution containing additive；
The metal material includes metal, alloy or the metallic composite that alloying reaction can occur with lithium ion；
The additive includes that can decompose and form the substance of SEI film in the metal material surface.
It should be understood that
" metal, alloy or metallic composite that alloying reaction can occur with lithium ion " is to refer to and lithium ion
The metal of alloying reaction occurs, the alloy material of alloying reaction can occur with lithium ion or can be closed with lithium ion
The metal composite conductive material of aurification reaction.
" alloy " refers to metal and metal by two or more or nonmetallic synthesized by certain methods has
The substance of metallic character.
" metallic composite " refers to that metal is formed by metal-based compound conductive material in conjunction with other nonmetallic materials.
Typical but non-limiting metallic composite includes graphene-metallic composite, carbon fiber reinforced metal matrix composite or pottery
Porcelain-metallic composite etc..
" material for being capable of providing lithium source " refers to the material containing lithium, and the lithium in material is in half-cell charge or discharge
It can be entered in electrolyte in the form of lithium ion in the process, and then alloying reaction occurs with working electrode and forms metal material
With the alloy of lithium.
It should be understood that the standard electrode potential of different " material for being capable of providing lithium source " is different, work as normal electrode
When current potential is lower than working electrode, which carries out electric discharge to half-cell to realize metal material
Pre- embedding lithium；When standard electrode potential is higher than working electrode, which fills half-cell
Electricity is to realize the pre- embedding lithium of metal material.
" can decompose and form SEI film in the metal material surface " is referred in half-cell charge or discharge process
Then middle decomposition forms SEI passivating film in the metal material surface.
It uses metal material as working electrode in the preparation method of above-mentioned pre- embedding cathode of lithium, be capable of providing the material of lithium source
Charge or discharge are carried out as the half-cell assembled to electrode and the lithium salt solution for containing additive as electrolyte.
The working mechanism of above-mentioned pre- embedding lithium are as follows: during charge or discharge, the additive in electrolyte decomposes first, thus in metal
Material surface forms SEI passivating film, and during further progress charge or discharge, lithium ion passes through passivating film and metal material
Alloying reaction occurs, the alloy of metal material and lithium is formed, to complete the process of pre- embedding lithium.To electrode primarily to mentioning
For the lithium source of pre- embedding lithium；It is pre- embedding cathode of lithium after the completion of pre- embedding lithium using the working electrode of metal material.
SEI (Solid Electrolyte Interface) film refers to " solid electrolyte interface film ", is formed in energy storage
Device is for the first time that electrode material and electrolyte react on solid-liquid phase interface, so that one layer formed covers in discharge process
It is placed on the passivation layer of electrode material surface.SEI film can be stabilized in organic solvent, and can effectively prevent solvent molecule
Pass through, solvent molecule is avoided to react the destruction for causing electrode material with electrode material；And Li+It but can be free by the SEI film
Ground insertion and abjection, will not charge and discharge to battery and cycle performance generate adverse effect.
It is above method simple process, low in cost.The SEI passivating film formed in above-mentioned pre- process of intercalation is conducive to improve negative
The stability of pole reduces the volume expansion that cathode generates during alloying/removal alloying occurs with lithium ion, avoids
Cathode is by dusting, and the alloy that pre- embedding lithium is formed helps to improve the coulombic efficiency of cathode, improves discharge capacity and cycle performance.
In addition, metal material is used as negative electrode active material and negative current collector simultaneously due to the metal material that cathode is pre- embedding lithium, it can
The self weight for effectively mitigating cathode, further increases the energy density and specific capacity of energy storage device.
It is preferably carried out in mode in one kind, the metal is in aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth
Any one；
Or, the alloy is including at least any one in aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth
Alloy；
Or, the metallic composite is including at least appointing in aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth
The composite material of one kind of anticipating.
Above-mentioned alloy is typical but non-limiting to be closed for mock silver, magnesium-zinc alloy, copper-iron alloy, Nitinol, manganese antimony
Gold, antimony bismuth alloy, aluminium tin magnesium alloy, zinc-copper ferroalloy, NiTi manganese alloy or manganese antimony bismuth alloy etc..Above-mentioned metallic composite allusion quotation
Type but it is unrestricted be aluminium/graphene composite foil, tin/graphene composite foil, magnesium/graphene composite foil or zinc/stone
Black alkene composite foil etc..
Further, the metal material with a thickness of 10~1000 μm.The thickness of above-mentioned metal material is typical but non-limit
Property processed is 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μ
M, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm or 1000 μm.
It should be noted that the form of above-mentioned metal material is preferably foil, the form for the pre- embedding cathode of lithium being prepared
Preferably sheet.
It is preferably carried out in mode in one kind, the material for being capable of providing lithium source includes the compound of lithium metal or lithium.
Above-mentioned " compound of lithium " refers to the substance of lithium and other one or more kinds of element compositions.
Preferably, the compound of the lithium includes lithium sulfide, lithia, lithium selenide, lithium fluoride, lithium oxalate, cobalt acid lithium, carbon
At least one of sour lithium or LiFePO4.The typical but non-limiting compound of above-mentioned lithium is lithium sulfide, lithia, selenizing
The combination of lithium, lithium fluoride, lithium oxalate, cobalt acid lithium, lithium carbonate, LiFePO4, lithium sulfide and lithia, lithium selenide and lithium fluoride
Combination, the combination of lithium oxalate and cobalt acid lithium, the combination of lithium carbonate and LiFePO4, the combination of lithium sulfide, lithia and lithium selenide,
The combination of lithium fluoride, lithium oxalate and cobalt acid lithium, or, cobalt acid lithium, lithium carbonate and combination of LiFePO4 etc..
Preferably, described is lithium metal to electrode, is discharged using lithium metal as the half-cell to electrode.Lithium metal
Standard electrode potential be lower than working electrode standard electrode potential, therefore using lithium metal be used as to electrode in half-cell actually
It for cathode, discharges the half-cell, the lithium ion in lithium metal can dissolve in electrolyte, to the metal material of working electrode
Material carries out pre- embedding lithium.
Preferably, described is the compound of lithium to electrode, is filled to using the compound of lithium as the half-cell to electrode
Electricity.The standard electrode potential of the compound of lithium be higher than working electrode standard electrode potential, therefore using the compound of lithium as pair
Electrode is actually anode in half-cell, is charged to the half-cell, the lithium ion in the compound of lithium can deviate from entrance
In electrolyte, pre- embedding lithium is carried out to the metal material of working electrode.
It should be noted that when using the compound of lithium as to electrode, to including electrode material and electrode collection in electrode
Fluid, electrode material include electrode active material, solvent, conductive agent and binder etc., and wherein electrode active material is above-mentioned lithium
Compound, the present invention is not particularly limited above-mentioned electrode current collecting body, solvent, conductive agent and binder, using the prior art
In.
It is preferably carried out in mode in one kind, the additive includes LiBOB, LiODFB, LiPO2F2、 LiDFOP、
At least one of LiBMB, LiDFMFMB, LiDFEFMB, LiDFPFMB or LiTFOP.LiBOB is dioxalic acid lithium borate,
LiODFB is difluorine oxalic acid boracic acid lithium, LiPO2F2For difluorophosphate, LiDFOP is the double oxalic acid lithium phosphates of difluoro, LiBMB bis- third
Diacid lithium borate, LiDFMFMB are two fluoro- 2- methyl -2- fluoromalonic acid lithiums, and LiDFEFMB is two fluoro- 2- ethyl -2- fluorine
For Lithium malonate, LiDFPFMB is two fluoro- 2- propyl -2- fluoromalonic acid lithiums, and LiTFOP is tetrafluoro oxalic acid lithium phosphate.It is above-mentioned to add
Add agent easily decomposes in half-cell charge or discharge, and can be formed in metal material surface after decomposing stable and function admirable
SEI passivating film.
Typical but non-limiting above-mentioned additive is LiBOB, LiODFB, LiPO2F2, LiDFOP, LiBMB,
The combination of LiDFMFMB, LiDFEFMB, LiDFPFMB, LiTFOP, LiBOB and LiODFB, LiPO2F2With the combination of LiDFOP,
The combination of the combination of the combination of LiBMB and LiDFMFMB, LiDFEFMB and LiDFPFMB, LiDFPFMB and LiTFOP, LiBOB,
LiODFB and LiPO2F2Combination, the combination of LiDFOP, LiBMB and LiDFMFMB, or, LiDFEFMB, LiDFPFMB and
The combination etc. of LiTFOP.
It is preferably carried out in mode in one kind, the mass fraction of the additive in the electrolytic solution is 0.1%-30%, excellent
It is selected as 8%-15%.It is 0.1% that above-mentioned mass fraction is typical but non-limiting, 0.5%, 1%, 2%, 4%, 6%, 8%,
10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28% or 30%.By the quality for adjusting additive
Number can regulate and control the thickness of SEI film.When the mass fraction of additive is 0.1%-30%, the thickness of SEI film is more closed
Reason reduces irreversible capacitance loss of the cathode when discharging for the first time, guarantees that cathode is with good stability, while will not shadow
Ring the chemical property of cathode.
Further, above-mentioned lithium salts includes lithium hexafluoro phosphate, LiBF4, lithium chloride, lithium carbonate, lithium sulfate, nitric acid
In lithium, lithium fluoride, trifluoromethanesulfonic acid lithium, bis- (trifluoromethyl sulfonyl) imine lithiums, double fluorine sulfimide lithiums or lithium perchlorate
It is at least one.Typical but non-limiting above-mentioned lithium salts is lithium hexafluoro phosphate, LiBF4, lithium chloride, lithium carbonate, sulfuric acid
Lithium, lithium nitrate, lithium fluoride, trifluoromethanesulfonic acid lithium, bis- (trifluoromethyl sulfonyl) imine lithiums, double fluorine sulfimide lithiums, perchloric acid
The combination of the combination of the combination of lithium, lithium hexafluoro phosphate and LiBF4, lithium chloride and lithium carbonate, lithium sulfate and lithium nitrate, fluorine
Change the combination of lithium and trifluoromethanesulfonic acid lithium, the combination of bis- (trifluoromethyl sulfonyl) imine lithiums and double fluorine sulfimide lithiums, hexafluoro
The combination of lithium phosphate, LiBF4 and lithium chloride, the combination of lithium carbonate, lithium sulfate and lithium nitrate, lithium fluoride, trifluoromethanesulfonic acid
The combination of lithium and bis- (trifluoromethyl sulfonyl) imine lithiums, or, bis- (trifluoromethyl sulfonyl) imine lithiums, double fluorine sulfimide lithiums
With the combination of lithium perchlorate etc..
Further, in the electrolyte, the concentration of lithium salts is 0.1-10mol/L.The concentration of above-mentioned lithium salts is typical but non-
It is restrictive for 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L,
4mol/L、4.5mol/L、5mol/L、5.5mol/L、6 mol/L、6.5mol/L、7mol/L、7.5mol/L、8mol/L、
8.5mol/L, 9mol/L, 9.5mol/L or 10mol/L.
Further, the solvent of electrolyte includes propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate
(DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), N, N- dimethyl second
Amide (DMA), fluorinated ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), γ-Ding Nei
Ester (GBL), tetrahydrofuran (THF), 2- methyltetrahydrofuran (2MeTHF), 1,3- dioxolanes (DOL), 4- methyl-1,3-
Dioxolanes (4MeDOL), dimethoxymethane (DMM), 1,2- diformazan Ethylene Oxide (DMP), triethylene glycol dimethyl ether (DG), two
Methyl sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), sulfurous acid propylene rouge (PS), two formicester of sulfurous acid (DMS),
At least one of sulfurous acid diethyl rouge (DES) or crown ether (12-crown-4).
Typical but non-limiting above-mentioned solvent is propene carbonate, ethylene carbonate, diethyl carbonate, carbonic acid diformazan
Ester, methyl ethyl carbonate, methyl formate, methyl acetate, n,N-dimethylacetamide, fluorinated ethylene carbonate, methyl propionate, propionic acid
Ethyl ester, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofuran, 1,3- dioxolanes, 4- methyl-1,3- bis-
Oxygen pentamethylene, dimethoxymethane, 1,2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, sulfurous acid ethylene
Ester, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, crown ether (12-crown-4), propene carbonate and ethylene carbonate
The combination of the combination of the combination of ester, diethyl carbonate and dimethyl carbonate, methyl ethyl carbonate and methyl formate, methyl acetate and N,
The combination of the combination of the combination of N- dimethyl acetamide, fluorinated ethylene carbonate and methyl propionate, ethyl propionate and ethyl acetate,
The combination of gamma-butyrolacton and tetrahydrofuran, 2- methyltetrahydrofuran and 1, the combination of 3- dioxolanes, 4- methyl-1,3- bis-
The combination of oxygen pentamethylene and dimethoxymethane, the combination of 1,2- diformazan Ethylene Oxide and triethylene glycol dimethyl ether, dimethyl sulfone and two
The combination of methyl ether, the combination of ethylene sulfite and sulfurous acid propylene rouge, the combination of two formicester of sulfurous acid and sulfurous acid diethyl rouge,
The combination of propene carbonate, ethylene carbonate and diethyl carbonate, the group of dimethyl carbonate, methyl ethyl carbonate and methyl formate
It closes, the combination of methyl acetate, n,N-dimethylacetamide and fluorinated ethylene carbonate, methyl propionate, ethyl propionate and acetic acid second
The combination of ester, the combination of gamma-butyrolacton, tetrahydrofuran and 2- methyltetrahydrofuran, 1,3- dioxolanes, 4- methyl-1,3-
The combination of dioxolanes and dimethoxymethane, the combination of 1,2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether and dimethyl sulfone, two
The combination of methyl ether, ethylene sulfite and sulfurous acid propylene rouge, or, two formicester of sulfurous acid, sulfurous acid diethyl rouge and crown ether (12-
Crown- 4) combination etc..
It is preferably carried out in mode in one kind, the electric current of charge or discharge is 0.01-1mA/cm2, charge or discharge when
Between be 100-1 hours.
The typical but non-limiting electric current of above-mentioned charge or discharge is 0.01mA/cm2、0.1mA/cm2、 0.2mA/cm2、
0.3mA/cm2、0.4mA/cm2、0.5mA/cm2、0.6mA/cm2、0.7mA/cm2、 0.8mA/cm2、0.9mA/cm2Or 1mA/cm2。
By adjusting the size of current of charge or discharge, the thickness of SEI film can be regulated and controled.When the electric current of charge or discharge is 0.01-
1mA/cm2When, the thickness of SEI film is relatively reasonable, reduces irreversible capacitance loss of the cathode when discharging for the first time, guarantees cathode
It is with good stability, while will not influence the chemical property of cathode.
It is 100 hours that the time of above-mentioned charge or discharge is typical but non-limiting, 95 hours, 90 hours, 85 hours, 80
Hour, 75 hours, 70 hours, 65 hours, 60 hours, 55 hours, 50 hours, 45 hours, 40 hours, 35 hours, 30 hours,
25 hours, 20 hours, 15 hours, 10 hours, 5 hours or 1 hour.By adjusting the time of charge or discharge, can regulate and control pre-
The depth of embedding lithium.When the time of charge or discharge is 100-1 small, the depth of pre- embedding lithium is relatively reasonable in metal material, guarantees
Cathode coulombic efficiency with higher, improves the discharge capacity of energy storage device.
Further, the pre- embedding cathode of lithium preparation method the following steps are included:
(a) metal foil of required size is spare as working electrode；
(b) using the lithium metal of required size as spare to electrode；
(c) it is spare to prepare the electrolyte containing additive；
(d) half-cell is assembled by working electrode, to electrode and electrolyte；
(e) it discharges half-cell, the metal foil of the pre- embedding lithium obtained after the completion of electric discharge is pre- embedding cathode of lithium.
Further, half-cell further includes diaphragm, and the diaphragm includes but is not limited to glass fibre, polyethylene diagrams, gathers
Propylene diaphragm or polypropylene, polyethylene/polypropylene diaphragm etc..
It is as shown in Figure 1 a kind of structural schematic diagram of half-cell, working electrode 1 and to there is half-cell electrolysis between electrode 2
Liquid 3 and half-cell diaphragm 5, half-cell electrolytes 3 are in contact with working electrode 1, and half-cell diaphragm 5 is in contact with to electrode 2.
Second aspect provides a kind of preparation method preparation using above-mentioned pre- embedding cathode of lithium at least one embodiment
Obtained pre- embedding cathode of lithium.
Cost is relatively low for the pre- embedding cathode of lithium obtained using the preparation method of above-mentioned pre- embedding cathode of lithium, and stabilization with higher
Property, the volume expansion generated during alloying/removal alloying occurs with lithium ion is small, is not easy by dusting, coulomb
Effect is high, good cycle, and the cathode has the advantages that self weight is low, can further increase the energy density of energy storage device with
Specific capacity.
The third aspect provides a kind of energy storage device at least one embodiment, including uses above-mentioned pre- embedding cathode of lithium
The pre- embedding cathode of lithium that is prepared of preparation method.The energy storage device includes being prepared using the preparation method of above-mentioned pre- embedding cathode of lithium
Made of pre- embedding cathode of lithium, thus have that device cost is cheap, stable structure, coulombic efficiency are high, discharge capacity is high, energy density
The advantages of high and good cycle.
Above-mentioned energy storage device includes but is not limited to lithium ion battery, Dual-ion cell or lithium-ion capacitor etc..
The core of above-mentioned energy storage device be include using above-mentioned pre- embedding cathode of lithium preparation method be prepared it is pre- embedding
Cathode of lithium, in addition to this, the energy storage device further include the other assemblies or component of existing energy storage device, for example, negative with pre- embedding lithium
Anode, electrolyte, diaphragm and shell that pole matches etc., the present invention is to this and is not particularly limited；In addition, the energy storage device
Preparation method is prepared using existing preparation method, and the present invention is to this and is not particularly limited.
Preferably, energy storage device is lithium ion battery, and positive electrode includes LiMn2O4, cobalt acid lithium, LiFePO4 or ternary
At least one of material.Wherein ternary material includes nickel-cobalt-manganese ternary material and/or nickel cobalt aluminium ternary material.
Preferably, energy storage device is lithium-ion capacitor, positive electrode include active carbon, carbon nanotube, activated carbon fiber,
At least one of graphene, mesoporous carbon, carbon molecular sieve or carbon foams.
Preferably, energy storage device is Dual-ion cell, and positive electrode includes natural graphite and/or expanded graphite.
Illustratively, plus plate current-collecting body include in aluminium, copper, iron, tin, zinc, nickel, titanium or manganese any one or at least contain
The alloy of any one of the above metallic element, or the metallic composite at least containing any one of the above metallic element.
Illustratively, energy storage device the preparation method is as follows:
(a) positive electrode active materials, conductive agent and binder are weighed by a certain percentage, and solvent is added later and is sufficiently mixed shape
At uniform sizing material；Wherein, in slurry, the mass content of positive electrode active materials is 60%-95%, and the mass content of conductive agent is
5%-30%, the mass content of binder are 5%-10%；
(b) slurry is evenly applied to plus plate current-collecting body surface, anode active material layer is formed, after being completely dried
It suppresses and cuts, obtain the energy storage device anode of required size；
(c) conventional electrolyte is prepared, the additive of certain mass score is added；
(d) using the pre- embedding cathode of lithium that is prepared of preparation method using above-mentioned pre- embedding cathode of lithium as cathode, pass through painting
The pole piece of piece preparation is as anode assembly energy storage device.
Additive in step (c) is conventional electrolysis additive, including esters, sulfone class, ethers, nitrile and alkene
Class organic solvent, including fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1,3-propane sultone, Isosorbide-5-Nitrae-
Butyl sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite, dimethyl
At least one of sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester or dimethyl sulfoxide.
It is illustrated in figure 2 a kind of energy storage device, including pre- embedding cathode of lithium 6, the energy storage device diaphragm 9, energy storage set gradually
Device electrolyte 7, positive active material 10 and plus plate current-collecting body 11.
Fourth aspect provides a kind of energy-storage system, including above-mentioned energy storage device at least one embodiment.The energy storage
System includes above-mentioned energy storage device, thus at least has advantage identical with above-mentioned energy storage device, with low in cost, structure is steady
The advantages of fixed, coulombic efficiency height, specific capacity height, energy density height and good cycle.
Above-mentioned energy-storage system refers to the electric power storage system for mainly using above-mentioned energy storage device as electric power storage source, including
But it is not limited to household energy-storage system or distributed energy storage system etc..For example, being stored in electric power in household energy-storage system and being used as
In the above-mentioned energy storage device of electric power storage source, and the electric power that consumption is stored in above-mentioned energy storage device as needed is can make
With the various devices of such as domestic electronic appliances.
5th aspect, provides a kind of electrical equipment, including above-mentioned energy storage device at least one embodiment.The electricity consumption
Equipment includes above-mentioned energy storage device, thus at least has advantage identical with above-mentioned energy storage device, has low in cost, specific capacity
The advantages of high, energy density height and good cycle, which makes under identical charging and discharging currents and identical environment
Used time, the service life is longer.
Above-mentioned electrical equipment includes but is not limited to electronic device, electric tool or electric vehicle etc..Electronic device be using
Above-mentioned energy storage device performs various functions the electronic device of (for example, performing music) as operation power.Electric tool be using
Electric tool of the above-mentioned energy storage device as driving power moving parts (for example, drill bit).Electric vehicle is by above-mentioned energy storage
The electric vehicle (including electric bicycle, electric car) that device is run as driving power, and can be in addition to above-mentioned storage
The automobile (including hybrid electric vehicle) of other driving sources is also equipped with except energy device.
Below with reference to embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
A kind of preparation method of pre- embedding cathode of lithium, comprising the following steps:
A) aluminium foil with a thickness of 50 μm is taken, the disk that diameter is 12mm is cut into, is cleaned with acetone, ethyl alcohol, dry postposition
It is spare as working electrode in glove box；
B) a certain amount of lithium hexafluoro phosphate is weighed in glove box, and is added to ethylene carbonate, dimethyl carbonate and carbon
In the mixture of diethyl phthalate (three's volume ratio is 1:1:1), it is configured to the lithium hexafluorophosphate electrolyte solution of 1M；
C) a certain amount of difluorine oxalic acid boracic acid lithium is weighed, is stirred to being completely dissolved, being configured to last additive level is
The electrolyte of 10wt.%；
D) all-glass paper is cut into the disk that diameter is 16mm, 80 DEG C of vacuum drying 12h are placed in glove box and make
It is spare for diaphragm；
E) in the glove box of argon atmosphere, by lithium metal, diaphragm, metal aluminium electrode, successively Close stack, dropwise addition are electrolysed
Liquid makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into shell, then carries out the pre- embedding lithium that discharges, and the electric current of electric discharge is big
Small is 0.02mA/cm2, discharge time 15h obtains the metal aluminium electrode of pre- embedding lithium, which is pre- embedding cathode of lithium.
Embodiment 2-13
A kind of preparation method of pre- embedding cathode of lithium, unlike the first embodiment, difluorine oxalic acid boracic acid lithium in embodiment 2-13
Mass fraction in the electrolytic solution is different, other steps and its parameter are identical as embodiment 1.
Lithium-ion capacitor including the pre- embedding cathode of lithium being prepared in embodiment 1-13, preparation method include following step
It is rapid:
A) a certain amount of lithium hexafluoro phosphate is weighed in glove box, and is added to ethylene carbonate, dimethyl carbonate and carbon
In the mixture of diethyl phthalate (three's volume ratio is 1:1:1), it is configured to the lithium hexafluorophosphate electrolyte solution of 1M；
B) 0.8g active carbon (AC), 0.1g conductive carbon black, 0.1g Kynoar are added to 2mL N- crassitude
In ketone, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface, 80 DEG C are dried in vacuo 12 hours；It is right
Dry the electrode obtained piece cuts into the disk that diameter is 10mm, is compacted (10MPa, 10s) with hydraulic press, is placed in conduct in glove box
Anode is spare；
C) by anode, diaphragm, cathode successively Close stack, electrolyte, which is added dropwise, makes diaphragm complete wetting, then by above-mentioned heap
Folded partial encapsulation enters shell, completes the assembling of capacitor.
Above-mentioned lithium-ion capacitor is tested for the property using the current density of 0.8A/g respectively, test result is shown in Table 1.
Table 1: the performance parameter table of the lithium-ion capacitor including the embodiment 1-13 pre- embedding cathode of lithium being prepared
Embodiment 14-21
A kind of preparation method of pre- embedding cathode of lithium, unlike the first embodiment, the addition of electrolyte in embodiment 14-21
The type of agent is different, other steps and its parameter are same as Example 1.
The pre- embedding cathode of lithium that embodiment 14-21 is prepared is prepared into lithium-ion capacitor, the same embodiment of preparation method
1, above-mentioned lithium-ion capacitor is tested for the property using the current density of 0.8A/g respectively, test result is shown in Table 2.
Table 2: the performance parameter table of the lithium-ion capacitor including the embodiment 14-21 pre- embedding cathode of lithium being prepared
Embodiment 22-30
A kind of preparation method of pre- embedding cathode of lithium, unlike the first embodiment, the metal material used in embodiment 22-30
The type of material is different, other steps and its parameter are same as Example 1.
The pre- embedding cathode of lithium that embodiment 22-30 is prepared is prepared into lithium-ion capacitor, the same embodiment of preparation method
1, above-mentioned lithium-ion capacitor is tested for the property using the current density of 0.8A/g respectively, test result is shown in Table 3.
Table 3: the performance parameter table of the lithium-ion capacitor including the embodiment 22-30 pre- embedding cathode of lithium being prepared
Embodiment 31
A kind of preparation method of pre- embedding cathode of lithium, unlike the first embodiment, by lithium carbonate in the present embodiment step 5)
Electrode, diaphragm, metal aluminium electrode successively Close stack, carry out the pre- embedding lithium that charges, and the size of current of charging is 0.02mA/cm2, fill
The electric time is 15h；Carbonic acid lithium electrode includes electrode current collecting body aluminium foil and using lithium carbonate as the electrode material of active material；Remaining step
Rapid and its parameter is identical as embodiment 1.
Embodiment 32-38
A kind of preparation method of pre- embedding cathode of lithium as different from Example 31 distinguishes the lithium carbonate in embodiment 31
Lithium sulfide, lithia, lithium selenide, lithium fluoride, lithium oxalate, cobalt acid lithium and LiFePO4 are replaced with, remaining step and its parameter are equal
It is identical as embodiment 32.
The pre- embedding cathode of lithium that embodiment 31-38 is prepared is prepared into lithium-ion capacitor, the same embodiment of preparation method
1, above-mentioned lithium-ion capacitor is tested for the property using the current density of 0.8A/g respectively, test result is shown in Table 4.
Table 4: the performance parameter table of the lithium-ion capacitor including the embodiment 31-38 pre- embedding cathode of lithium being prepared
Dual-ion cell including the embodiment 1-13 pre- embedding cathode of lithium being prepared, preparation method the following steps are included:
A) a certain amount of lithium hexafluoro phosphate is weighed in glove box, and is added to ethylene carbonate, dimethyl carbonate and carbon
In the mixture of diethyl phthalate (three's volume ratio is 1:1:1), it is configured to the lithium hexafluorophosphate electrolyte solution of 1M；
B) 0.8g natural graphite (NG), 0.1g conductive carbon black, 0.1g Kynoar are added to 2mL N- methylpyrrole
In alkanone, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface, 80 DEG C are dried in vacuo 12 hours；
The disk that diameter is 10mm is cut into dry the electrode obtained piece, (10MPa, 10s) is compacted with hydraulic press, is placed in glove box
It is spare as anode；
C) by anode, diaphragm, cathode successively Close stack, electrolyte, which is added dropwise, makes diaphragm complete wetting, then by above-mentioned heap
Folded partial encapsulation enters shell, completes the assembling of Dual-ion cell.
Above-mentioned Dual-ion cell is tested for the property using the current density of 0.8A/g respectively, test result is shown in Table 5.
Table 5: the performance parameter table of the Dual-ion cell including the embodiment 1-13 pre- embedding cathode of lithium being prepared
Lithium ion battery including the embodiment 1-13 pre- embedding cathode of lithium being prepared, preparation method the following steps are included:
A) a certain amount of lithium hexafluoro phosphate is weighed in glove box, and is added to ethylene carbonate, dimethyl carbonate and carbon
In the mixture of diethyl phthalate (three's volume ratio is 1:1:1), it is configured to the lithium hexafluorophosphate electrolyte solution of 1M；
B) 0.8g LiFePO4,0.1g conductive carbon black, 0.1g Kynoar are added to 2mL N- methyl pyrrolidone
In, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface, 80 DEG C are dried in vacuo 12 hours；To dry
Dry the electrode obtained piece cuts into the disk that diameter is 10mm, is compacted (10MPa, 10s) with hydraulic press, is placed in glove box as just
It is extremely spare；
C) by anode, diaphragm, cathode successively Close stack, electrolyte, which is added dropwise, makes diaphragm complete wetting, then by above-mentioned heap
Folded partial encapsulation enters shell, completes the assembling of lithium ion battery.
Above-mentioned lithium ion battery is tested for the property using the current density of 0.8A/g respectively, test result is shown in Table 6.
Table 6: the performance parameter table of the lithium ion battery including the embodiment 1-13 pre- embedding cathode of lithium being prepared
Comparative example 1
A kind of preparation method of pre- embedding cathode of lithium is free of difluoro unlike the first embodiment in the electrolyte of this comparative example
Lithium bis (oxalate) borate additive.
The pre- embedding cathode of lithium that comparative example 1 is prepared is prepared into lithium-ion capacitor, and the preparation method is the same as that of Example 1, right
Above-mentioned lithium-ion capacitor is tested for the property using the current density of 0.8A/g, and after tested, 500 capacity of capacitor cycle are protected
Holdup is 70%, coulombic efficiency 89.2%, energy density 150Wh/kg, specific capacitance 115F/g, and the above performance is below
Embodiment 1.
It is illustrated in figure 3 embodiment 1 and the pre- embedding lithium discharge curve of comparative example 1, can be seen that in embodiment 1 from curve
Containing LiODFB, there are apparent reduction peaks to illustrate aluminium gold metal surface corresponding to the decomposition of LiODFB in electric discharge for embodiment 1
The formation of passivating film, and LiODFB is free of in comparative example 1, LiODFB decomposable process is not present in electric discharge.
Fig. 4 (a) and Fig. 4 (b) is respectively the surface topography for the pre- embedding cathode of lithium that comparative example 1 and embodiment 1 obtain, comparative example
1 and embodiment 1 in be all 50 μm of aluminium foil used in negative electrode material, it can be seen that LiODFB, cathode table are free of in comparative example 1
Face particle is larger, and embodiment 1 contains LiODFB, and negative terminal surface particle is tiny and uniform, illustrates to form well-formed's
SEI film.
Comparative example 2
A kind of preparation method of pre- embedding cathode of lithium, unlike the first embodiment, the additive in the electrolyte of this comparative example
For lithium nitrate, lithium nitrate can not form SEI film in metal material surface.
The pre- embedding cathode of lithium that comparative example 2 is prepared is prepared into lithium-ion capacitor, and the preparation method is the same as that of Example 1, right
Above-mentioned lithium-ion capacitor is tested for the property using the current density of 0.8A/g, and after tested, 500 capacity of capacitor cycle are protected
Holdup is 63%, coulombic efficiency 69.1%, energy density 128Wh/kg, specific capacitance 97F/g, and the above performance is below reality
Apply example 1.
Comparative example 3
A kind of preparation method of pre- embedding cathode of lithium, comprising the following steps:
A) aluminium foil with a thickness of 50 μm is taken, the disk that diameter is 12mm is cut into, is cleaned with acetone, ethyl alcohol, dry postposition
It is spare as working electrode in glove box；
B) a certain amount of lithium hexafluoro phosphate is weighed in glove box, and is added to ethylene carbonate, dimethyl carbonate and carbon
In the mixture of diethyl phthalate (three's volume ratio is 1:1:1), it is configured to the lithium hexafluorophosphate electrolyte solution of 1M；
C) after slurry being made in active material lithium carbonate and additive difluorine oxalic acid boracic acid lithium (the two mass ratio is 9:1)
It is spare as carbonic acid lithium electrode coated in drying in current collector aluminum foil；
D) all-glass paper is cut into the disk that diameter is 16mm, 80 DEG C of vacuum drying 12h are placed in glove box and make
It is spare for diaphragm；
E) in the glove box of argon atmosphere, carbonic acid lithium electrode, diaphragm, metal aluminium electrode successively Close stack are added dropwise
Electrolyte makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into shell, then carries out the pre- embedding lithium that charges, the electricity of charging
Stream size is 0.02mA/cm2, charging time 15h obtains the metal aluminium electrode of pre- embedding lithium, which is pre- embedding cathode of lithium.
As different from Example 31, difluorine oxalic acid boracic acid lithium additive has been added to in electrode by this comparative example.
The pre- embedding cathode of lithium that comparative example 3 is prepared is prepared into lithium-ion capacitor, and the preparation method is the same as that of Example 1, right
Above-mentioned lithium-ion capacitor is tested for the property using the current density of 0.8A/g, and after tested, 500 capacity of capacitor cycle are protected
Holdup is 60%, coulombic efficiency 61.8%, energy density 131Wh/kg, specific capacitance 99F/g, and the above performance is below reality
Apply example 32.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of pre- embedding cathode of lithium, which is characterized in that provide a half-cell, to the half-cell carry out charging or
Electric discharge；
Wherein, the working electrode of the half-cell is metal material, is the material for being capable of providing lithium source to electrode, electrolyte be containing
There is the lithium salt solution of additive；
The metal material includes metal, alloy or the metallic composite that alloying reaction can occur with lithium ion；
The additive includes that can decompose and form the substance of SEI film in the metal material surface.
2. the preparation method of pre- embedding cathode of lithium according to claim 1, which is characterized in that the metal be aluminium, tin, magnesium,
Any one in zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth；
Or, the alloy is including at least the alloy of any one in aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth；
Or, the metallic composite is including at least any one in aluminium, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth
The composite material of kind；
Preferably, the metal material with a thickness of 10-1000 μm.
3. the preparation method of pre- embedding cathode of lithium according to claim 1, which is characterized in that the material for being capable of providing lithium source
Material includes the compound of lithium metal or lithium；
Preferably, the compound of the lithium includes lithium sulfide, lithia, lithium selenide, lithium fluoride, lithium oxalate, cobalt acid lithium, lithium carbonate
Or at least one of LiFePO4；
Preferably, described is lithium metal to electrode, is discharged using lithium metal as the half-cell to electrode；
Preferably, described is the compound of lithium to electrode, is charged to using the compound of lithium as the half-cell to electrode.
4. the preparation method of pre- embedding cathode of lithium according to claim 1, which is characterized in that the additive include LiBOB,
LiODFB、LiPO2F2, at least one of LiDFOP, LiBMB, LiDFMFMB, LiDFEFMB, LiDFPFMB or LiTFOP；
Preferably, the mass fraction of the additive in the electrolytic solution is 0.1%-30%, preferably 8%-15%；
Preferably, the lithium salts in electrolyte includes lithium hexafluoro phosphate, LiBF4, lithium chloride, lithium carbonate, lithium sulfate, nitric acid
In lithium, lithium fluoride, trifluoromethanesulfonic acid lithium, bis- (trifluoromethyl sulfonyl) imine lithiums, double fluorine sulfimide lithiums or lithium perchlorate
It is at least one；
Preferably, in the electrolyte, the concentration of lithium salts is 0.1-10mol/L；
Preferably, the solvent of the electrolyte includes at least one of esters, sulfone class, ethers, nitrile or olefines；
Preferably, the solvent of the electrolyte include propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC),
Dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), DMAC N,N' dimethyl acetamide
(DMA), fluorinated ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), gamma-butyrolacton
(GBL), tetrahydrofuran (THF), 2- methyltetrahydrofuran (2MeTHF), 1,3- dioxolanes (DOL), 4- methyl-1,3- bis-
Oxygen pentamethylene (4MeDOL), dimethoxymethane (DMM), 1,2- diformazan Ethylene Oxide (DMP), triethylene glycol dimethyl ether (DG), diformazan
Base sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), sulfurous acid propylene rouge (PS), two formicester of sulfurous acid (DMS), Asia
At least one of sulfuric acid diethyl ester (DES) or crown ether (12-crown-4).
5. the preparation method of pre- embedding cathode of lithium according to claim 1-4, which is characterized in that charge or discharge
Electric current is 0.01-1mA/cm2, the time of charge or discharge is 100-1 hours；
Preferably, the half-cell further includes diaphragm, the diaphragm include glass fibre, polyethylene diagrams, polypropylene diaphragm or
At least one of polypropylene, polyethylene/polypropylene diaphragm.
6. the pre- embedding cathode of lithium being prepared using the preparation method of the described in any item pre- embedding cathode of lithium of claim 1-5.
7. a kind of energy storage device, which is characterized in that including the preparation using the described in any item pre- embedding cathode of lithium of claim 1-5
The pre- embedding cathode of lithium that method is prepared.
8. energy storage device according to claim 7, which is characterized in that the energy storage device further includes positive electrode；
Preferably, energy storage device is lithium ion battery, and positive electrode includes LiMn2O4, cobalt acid lithium, LiFePO4 or ternary material
At least one of；
Preferably, energy storage device is lithium-ion capacitor, and positive electrode includes active carbon, carbon nanotube, activated carbon fiber, graphite
At least one of alkene, mesoporous carbon, carbon molecular sieve or carbon foams；
Preferably, energy storage device is Dual-ion cell, and positive electrode includes natural graphite and/or expanded graphite.
9. a kind of energy-storage system, which is characterized in that including energy storage device described in claim 7 or 8.
10. a kind of electrical equipment, which is characterized in that including energy storage device described in claim 7 or 8.
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| CN110078042B (en) * | 2019-04-30 | 2022-10-14 | 西南大学 | Lithium-rich lithium iron phosphate material and preparation method and application thereof |
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Application publication date: 20190426 Assignee: REAL POWER INDUSTRIAL Ltd. Assignor: SHENZHEN INSTITUTES OF ADVANCED TECHNOLOGY Contract record no.: X2022980016102 Denomination of invention: Preparation method of pre embedded lithium anode and prepared pre embedded lithium anode, energy storage device, energy storage system and electrical equipment Granted publication date: 20200717 License type: Exclusive License Record date: 20220922 |