CN108199044A - A kind of secondary cell and preparation method thereof - Google Patents

A kind of secondary cell and preparation method thereof Download PDF

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Publication number
CN108199044A
CN108199044A CN201711421169.4A CN201711421169A CN108199044A CN 108199044 A CN108199044 A CN 108199044A CN 201711421169 A CN201711421169 A CN 201711421169A CN 108199044 A CN108199044 A CN 108199044A
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China
Prior art keywords
secondary cell
anode
electrode active
positive electrode
electrolyte
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CN201711421169.4A
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Inventor
唐永炳
申京受
张帆
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Shenzhen Institute of Advanced Technology of CAS
University of Chinese Academy of Sciences
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Shenzhen Institute of Advanced Technology of CAS
University of Chinese Academy of Sciences
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Priority to CN201711421169.4A priority Critical patent/CN108199044A/en
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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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides a kind of secondary cells and preparation method thereof, including anode, cathode and the diaphragm and electrolyte being set between the anode and the cathode, the anode includes plus plate current-collecting body and the anode active material layer being arranged on the plus plate current-collecting body, the anode active material layer includes positive electrode active materials, and the positive electrode active materials include the organic material with reversible embedding de- lithium activity or reversible Doped anions activity；The cathode includes metal foil, and the metal foil is simultaneously as negative current collector and negative electrode active material.Its positive electrode active materials used is organic material, there is higher storage energy and abundant raw material, safe, environmentally protective compared to inorganic positive electrode, metal foil is simultaneously as negative current collector and negative electrode active material, significantly reduce the weight and volume of battery, the energy density of battery is improved, and the secondary cell has good charge-discharge performance.

Description

A kind of secondary cell and preparation method thereof
Technical field
The present invention relates to secondary battery technology, more particularly to a kind of secondary cell and preparation method thereof.
Background technology
Secondary cell is also referred to as rechargeable battery, is a kind of repeatable charge and discharge, using multiple battery.Compared to can not The one-shot battery of reuse, secondary cell have the advantages that use cost is low, environmental pollution is small.Current main secondary electricity There are lead-acid battery, Ni-Cr battery, Ni-MH battery, lithium ion battery in pond, wherein especially the most extensive with lithium ion battery applications.Day Mobile phone, laptop, digital camera often used etc. is all using lithium ion battery as power supply.The core composition of lithium ion battery Component generally comprises anode, cathode and electrolyte, it by the transmission of the ion that is happened on anode, cathode and electrolyte interface with Electron-transport phase separation redox reaction come realize power storage with release.Presently commercially available lithium ion battery mainly with Inorganic material is as positive electrode active materials.However, widely used inorganic positive electrode generally existing capacity boost is limited, production The process consumption energy is big, there are security risk and it is of high cost the defects of.It is more preferable therefore, it is necessary to develop specific capacity higher, safety With the green energy resource material of the reserves more horn of plenty in nature.
Invention content
In view of this, the present invention provides a kind of secondary cell, positive electrode active materials use, and there is reversible embedding de- lithium to live The organic material of property or reversible Doped anions activity, these organic materials have higher storage compared to inorganic positive electrode It is energy and abundant raw material, safe, environmentally protective, while using metal foil as negative current collector and negative electrode active material Material significantly reduces the weight and volume of battery, improves the energy density of battery, and the secondary cell has good fill Discharge cycle performance.
In a first aspect, the present invention provides a kind of secondary cell, including anode, cathode and be set to the anode with Diaphragm and electrolyte between the cathode, the anode include plus plate current-collecting body and are arranged on the plus plate current-collecting body just Pole active material layer, the anode active material layer include positive electrode active materials, and the positive electrode active materials include having reversible The organic material of embedding de- lithium activity or reversible Doped anions activity；The cathode includes metal foil, and the metal foil is same Shi Zuowei negative current collectors and negative electrode active material.
Optionally, the positive electrode active materials include conducting high polymers object, sulfur-containing compound, NO free radical chemical combination It is one or more in object, oxygen-containing conjugated compound.
Optionally, the conducting high polymers object includes polypyrrole, polyaniline, gathers in benzene, polyacetylene, polythiophene One or more, the sulfur-containing compound includes Allifridin, diallyl trisulfide, diallyl disulfide In it is one or more, the compound oxygen radical of nitrogen includes 2,2,6,6- tetramethyl piperidines-nitrogen-oxide and its polymer At least one of, the oxygen-containing conjugation organic matter includes one or more in quinones, the acid anhydrides containing conjugated structure. Further alternative, the quinones includes one in six quinone of dimer tetrahydrochysene, nonylbenzene and six quinones, anthraquinone and its polymer Kind is a variety of.
Optionally, the anode active material layer further includes conductive agent and binding agent, the conductive agent include conductive black, One or more in conductive carbon ball, electrically conductive graphite, carbon nanotube, conductive carbon fibre, graphene, the binding agent includes poly- inclined It is one or more in vinyl fluoride, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins.
Optionally, the mass content of positive electrode active materials described in the anode active material layer is 60%-90%, described The mass content of conductive agent is 2%-30%, and the mass content of the binding agent is 3%-10%.
Optionally, the material of the metal foil includes any one in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese or contains There are the alloy of at least one above-mentioned metallic element or the composite material containing at least one above-mentioned metallic element, the anode collection The material of fluid is including any one in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese or contains the above-mentioned metallic element of at least one Alloy or composite material containing at least one above-mentioned metallic element.It is further alternative, the material packet of the metal foil Include any one in aluminium, copper, iron, tin, zinc or the alloy containing at least one above-mentioned metallic element or containing at least one The composite material of above-mentioned metallic element.Further optional, the material of the metal foil includes aluminium.
Optionally, the electrolyte includes lithium salts and solvent, and the solvent is included in esters, sulfone class or ether organic solvent It is one or more.Optionally, a concentration of 0.1-10mol/L of lithium salts described in the electrolyte.In the present invention, the electricity Solvent in solution liquid can make the lithium salts be dissociated into lithium ion and anion, and can in the solvent free migration.Into One step is optional, and the lithium salts includes lithium hexafluoro phosphate, bis- (trimethyl fluoride sulfonyl) imine lithiums, LiBF4, fluoroform One or more in Sulfonic Lithium, lithium perchlorate, the solvent includes ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbon One or more in sour methyl ethyl ester, dimethyl sulfoxide (DMSO), dimethyl ether, propene carbonate, lithium salts is dense described in the electrolyte It spends for 1-4mol/L.Specifically, the concentration of lithium salts described in the electrolyte can be, but not limited to for 0.5mol/L, 1mol/L, 1.7mol/L、2mol/L、2.5mol/L、3mol/L、3.6mol/L、4mol/L、5mol/L.It is further optional, the lithium Salt includes lithium hexafluoro phosphate, and the solvent includes methyl ethyl carbonate, a concentration of 4mol/L of the lithium hexafluoro phosphate.
In the present invention, the raising of concentration of electrolyte can increase anion quantity, anion intercalated so as to be conducive to improve The specific capacity of anode, and then improve the energy density of battery.
Optionally, the electrolyte further includes additive, and the additive includes esters, sulfone class, ethers, nitrile and alkene One or more in class organic additive, mass fraction of the additive in the electrolyte is 0.1%-20%. In the present invention, the additive in electrolyte can form stable solid electrolyte film on the surface of negative current collector, prevent from bearing Pole collector in charge and discharge due to volume change caused by destruction, keep the stability of negative current collector, improve negative pole currect collecting The service life and performance of body improve the circulation ability of secondary cell.Further alternative, the organic additive includes carbonic acid Vinylene, fluorinated ethylene carbonate, glycol sulfite, propylene sulfite, ethyl sulfate, propylene sulfite, ring One or more in butyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, the additive is in the electrolyte Mass content is 2%-10%.Further optional, the organic additive includes vinylene carbonate, carbonic acid Asia second Mass content of the enester in the additive is 2%.
Optionally, the diaphragm is the porous polymer film of insulation or the inorganic porous film of insulation.It is further optional , the diaphragm includes porous polypropylene film, porous polyethylene film, porous compound polymer film, all-glass paper, more It is one or more in the ceramic membrane of hole.
The secondary cell that first aspect present invention provides, with reversible embedding de- lithium activity or reversible Doped anions activity Organic material as positive electrode active materials, these organic materials have higher storage energy compared to inorganic positive electrode, It is more safe and environmentally protective so as to improve the energy density of secondary cell, reduce manufacture cost.
Second aspect, the present invention provide a kind of preparation method of secondary cell, including：
Plus plate current-collecting body is provided, anode active material layer is prepared on the plus plate current-collecting body, is cut into after dry, compacting Required size obtains anode, and the anode active material layer includes positive electrode active materials, and the positive electrode active materials include having The organic material of reversible embedding de- lithium activity or reversible Doped anions activity；
Metal foil is cut into required size, after surface clean, drying, obtains cathode, the metal foil is same Shi Zuowei negative current collectors and negative electrode active material；
Electrolyte and diaphragm are provided, it is under inert gas or water-less environment, the cathode, diaphragm, anode is close successively It stacks, adding in the electrolyte makes the diaphragm complete wetting, and above-mentioned stacking portion then is encapsulated into battery case, obtains two Primary cell.
The preparation method for the secondary cell that second aspect of the present invention provides, it is simple for process, suitable for large-scale production.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification Or can be through the embodiment of the present invention implementation and know.
Description of the drawings
Fig. 1 is a kind of structure diagram of secondary cell provided in an embodiment of the present invention.
Specific embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art For art personnel, under the premise of principle of the embodiment of the present invention is not departed from, several improvements and modifications can also be made, these improvement The protection domain of the embodiment of the present invention is also considered as with retouching.
It is a kind of secondary cell provided in an embodiment of the present invention, including cathode 10, electrolyte 20,30 and of diaphragm with reference to Fig. 1 Anode 40, wherein anode 40 include plus plate current-collecting body 42 and the anode active material layer being arranged on the plus plate current-collecting body 42 41.The anode active material layer 41 includes positive electrode active materials, and the positive electrode active materials include that there is reversible embedding de- lithium to live The organic material of property or reversible Doped anions activity；The cathode 10 includes metal foil, metal foil conduct simultaneously Negative current collector and negative electrode active material.
In embodiments of the present invention, the positive electrode active materials include conducting high polymers object, sulfur-containing compound, nitrogen It is one or more in oxygen radical compound, oxygen-containing conjugated compound.
In embodiments of the present invention, the conducting high polymers object includes polypyrrole, polyaniline, gathers to benzene, poly- second One or more in alkynes, polythiophene, the sulfur-containing compound includes Allifridin, garlicin It is one or more in object, diallyl disulfide, the compound oxygen radical of nitrogen include 2,2,6,6- tetramethyl piperidines-nitrogen- At least one of oxide and its polymer, the oxygen-containing conjugation organic matter include quinones, the acid containing conjugated structure It is one or more in acid anhydride.Further alternative, the quinones includes six quinone of dimer tetrahydrochysene, nonylbenzene and six quinones, anthracene It is one or more in quinone and its polymer.
In embodiments of the present invention, the anode active material layer further includes conductive agent and binding agent, the conductive agent It is described including one or more in conductive black, conductive carbon ball, electrically conductive graphite, carbon nanotube, conductive carbon fibre, graphene Binding agent includes one in Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins Kind is a variety of.
In embodiments of the present invention, the mass content of positive electrode active materials described in the anode active material layer is 60%-90%, the mass content of the conductive agent is 2%-30%, and the mass content of the binding agent is 3%-10%.Into one Step, the mass content of positive electrode active materials described in the anode active material layer be 60%-85%, the matter of the conductive agent Amount content is 5%-25%, and the mass content of the binding agent is 5%-8%.
In embodiments of the present invention, the material of the metal foil is included in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese Any one or the alloy containing at least one above-mentioned metallic element or the composite wood containing at least one above-mentioned metallic element Material, the material of the plus plate current-collecting body include any one in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese or contain at least one The alloy of above-mentioned metallic element or the composite material containing at least one above-mentioned metallic element.It is further alternative, the metal The material of paillon include aluminium, copper, iron, tin, any one or the alloy containing at least one above-mentioned metallic element in zinc or Composite material containing at least one above-mentioned metallic element.Further optional, the material of the metal foil includes aluminium.
In embodiments of the present invention, the electrolyte includes lithium salts and solvent, and the solvent includes esters, sulfone class or ether It is one or more in class organic solvent.Optionally, a concentration of 0.1-10mol/L of lithium salts described in the electrolyte.At this In invention, the solvent in the electrolyte can make the lithium salts be dissociated into lithium ion and anion, and can be in the solvent Middle free migration.Further alternative, the lithium salts includes lithium hexafluoro phosphate, bis- (trimethyl fluoride sulfonyl) imine lithiums, tetrafluoro boron It is one or more in sour lithium, trifluoromethayl sulfonic acid lithium, lithium perchlorate, the solvent include ethylene carbonate, diethyl carbonate, It is one or more in dimethyl carbonate, methyl ethyl carbonate, dimethyl sulfoxide (DMSO), dimethyl ether, propene carbonate, in the electrolyte A concentration of 1-4mol/L of the lithium salts.Specifically, the concentration of lithium salts described in the electrolyte can be, but not limited to for 0.5mol/L、1mol/L、1.7mol/L、2mol/L、2.5mol/L、3mol/L、3.6mol/L、4mol/L、5mol/L.More into one Step is optional, and the lithium salts includes lithium hexafluoro phosphate, and the solvent includes methyl ethyl carbonate, the lithium hexafluoro phosphate it is a concentration of 4mol/L。
In the present invention, the raising of concentration of electrolyte can increase anion quantity, anion intercalated so as to be conducive to improve The specific capacity of anode, and then improve the energy density of battery.
In embodiments of the present invention, the electrolyte further includes additive, and the additive includes esters, sulfone class, ether One or more in class, nitrile and olefines organic additive, mass fraction of the additive in the electrolyte is 0.1%-20%.In the present invention, the additive in electrolyte can form stable solid electricity on the surface of negative current collector Plasma membrane is solved, is destroyed caused by preventing negative current collector in charge and discharge due to volume change, keeps the stability of negative current collector, The service life and performance of negative current collector are improved, improves the circulation ability of secondary cell.It is further alternative, it is described organic to add Agent is added to include vinylene carbonate, fluorinated ethylene carbonate, glycol sulfite, propylene sulfite, ethyl sulfate, sulfurous One or more in acid propylene ester, cyclobutyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, the additive is described Mass content in electrolyte is 2%-10%.Further optional, the organic additive includes vinylene carbonate, institute It is 2% to state mass content of the vinylene carbonate in the additive.
In embodiments of the present invention, the diaphragm be insulation porous polymer film or insulation it is inorganic porous thin Film.It is further alternative, the diaphragm include porous polypropylene film, porous polyethylene film, porous compound polymer film, It is one or more in all-glass paper, porous ceramic film.
The operation principle of above-mentioned secondary cell provided in an embodiment of the present invention is：In charging process, the moon in electrolyte In Ion transfer to anode and embedded positive electrode active materials, lithium ion mobility forms lithium-metal alloy to cathode and with cathode；It puts Anion is deviate to return in electrolyte from positive electrode active materials in electric process, and lithium ion returns to electrolyte from cathode removal alloying In, so as to fulfill entire charge and discharge process.With the organic material with reversible embedding de- lithium activity or reversible Doped anions activity As positive electrode active materials, improve the energy density of secondary cell, reduce manufacture cost, it is more safe and environmentally protective；This Outside, since negative metal paillon is simultaneously as negative electrode active material and collector so that battery weight and volume reduce, and battery holds Amount improves, and then improves battery energy density, and has saved battery production manufacture cost.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of above-mentioned secondary cell, includes the following steps：
(1) anode is prepared：Plus plate current-collecting body is provided, anode active material layer is prepared on the plus plate current-collecting body, dry, Required size is cut into after compacting, obtains anode, the anode active material layer includes positive electrode active materials, the positive-active Material includes the organic material with reversible embedding de- lithium activity or reversible Doped anions activity；
(2) cathode is prepared：Metal foil is cut into required size, after surface clean, drying, obtains cathode, institute State metal foil while as negative current collector and negative electrode active material；
(3) electrolyte is prepared：It weighs a certain amount of lithium salts electrolyte to be added in organic solvent, is sufficiently stirred dissolving, obtains Required electrolyte.
(4) diaphragm is prepared：Porous polymer film or inorganic porous film are cut into required size, after cleaning up, Obtain required diaphragm.
(5) battery assembles：Under inert gas or water-less environment, by the cathode, diaphragm, anode successively Close stack, Adding in the electrolyte makes the diaphragm complete wetting, and above-mentioned stacking portion then is encapsulated into battery case, obtains secondary electricity Pond.
It should be noted that although above-mentioned steps (1)-(4) are to describe secondary cell preparation side of the present invention with particular order The operation of method, still, it is not necessary to perform these operations according to the particular order.The operation of step (1)-(4) can be simultaneously Or arbitrary successively execution.
The raw material being applied in the above-mentioned preparation method of the embodiment of the present invention as described in the previous embodiment, herein no longer It repeats.
In embodiments of the present invention, the form of secondary cell is not limited, can be, but not limited to as button cell, side Shape battery, cylindrical battery, soft-package battery.Specifically, it is selected according to actual needs.
The preparation method that specific embodiment further illustrates above-mentioned secondary cell is set forth below.
Embodiment 1
A kind of secondary cell is present embodiments provided, including cathode, diaphragm, electrolyte and anode.Wherein, the secondary cell Specific material composition and preparation method it is as follows：
Prepare battery cathode：The aluminium foil that thickness is taken to be 0.05mm, cuts into the disk of diameter 12mm, is cleaned with ethyl alcohol, dried in the air It is dry spare as negative current collector.
Prepare diaphragm：All-glass paper is cut into the disk of diameter 16mm, is cleaned with acetone, it is standby as diaphragm after drying With.
Prepare electrolyte：It weighs 3g lithium hexafluoro phosphates to be added in 5mL methyl ethyl carbonates, stir complete to lithium hexafluoro phosphate Dissolving is configured to the electrolyte of a concentration of 4mol/L of lithium hexafluoro phosphate, then adds in the vinylene carbonate that mass fraction is 2% It is spare as electrolyte after stirring as additive.
Prepare anode：0.7g polyanilines, 0.2g carbon blacks, 0.1g Kynoar are added to 2mL N-methyl pyrroles In alkanone solution, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.To drying The electrode obtained piece cuts into the disk of diameter 10mm, spare as anode after compacting.
Battery assembles：In the glove box of inert gas shielding, by the above-mentioned negative current collector prepared, diaphragm, battery Close stack, dropwise addition electrolyte make diaphragm complete wetting, above-mentioned stacking portion then are encapsulated into button cell shell anode successively Body completes battery assembling, obtains secondary cell.
The reaction principle of the secondary cell of the embodiment of the present invention 1 is：Cathode：Anode：
Secondary cell obtained above is charged by the current density of 100mA/g, until its voltage reaches 4.2V, then With identical current discharge, until its voltage reaches 2V, its battery specific capacity and energy density are measured, tests its stable circulation Property.
Embodiment 2
The present embodiment provides a kind of secondary cell, wherein positive electrode active materials use polypyrrole, other and 1 phase of embodiment Together.
Embodiment 3
The present embodiment provides a kind of secondary cell, wherein positive electrode active materials use polythiophene, other and 1 phase of embodiment Together.
Embodiment 4
The present embodiment provides a kind of secondary cell, wherein positive electrode active materials use Allifridin, other It is same as Example 1.
Embodiment 5
The present embodiment provides a kind of secondary cell, wherein positive electrode active materials use 2,2,6,6- tetramethyl piperidines-nitrogen-oxygen Compound, other are same as Example 1.
Embodiment 6
The present embodiment provides a kind of secondary cell, wherein positive electrode active materials use anthraquinone, other are same as Example 1.
Comparative example 1
This comparative example is a kind of secondary cell, and wherein positive electrode active materials use native graphite, other and 1 phase of embodiment Together.
Comparative example 2
This comparative example is a kind of secondary cell, and wherein positive electrode active materials use expanded graphite, other and 1 phase of embodiment Together.
The secondary cell preparation process of embodiment 2-6, comparative example 1-2 and embodiment 1 is different except positive electrode active materials, other All steps and the material used are all identical, at the same to the 2C charge and discharge of the battery of embodiment 2-6 and comparative example 1-2 under the conditions of Specific discharge capacity, energy density and cyclical stability (represented with recycling the number of turns, under the conditions of the cycle number of turns refers to 2C charge and discharge, Battery institute charge and discharge number when battery capacity decays to 90%) it is tested, and compared with the performance of the embodiment of the present invention 1 Compared with referring specifically to table 1.
Secondary cell performance parameter table prepared by table 1 embodiment 1-6 and comparative example 1-2
As it can be seen from table 1 embodiment 1-5 uses having with reversible embedding de- lithium activity or reversible Doped anions activity Machine material, such as conducting high polymers object, sulfur-containing compound, compound oxygen radical of nitrogen, oxygen-containing conjugated compound etc., system The effect of the standby obtained specific capacity of secondary cell, energy density and the cycle number of turns than comparative example 1-2 is good, wherein using polyphenyl When amine is as positive electrode active materials, the secondary cell being prepared has better specific capacity, energy density and the cycle number of turns.
Embodiment 7
The present embodiment provides a kind of secondary cell, wherein cathode uses tinfoil paper, other are same as Example 1.
Embodiment 8
The present embodiment provides a kind of secondary cell, wherein cathode uses zinc foil, other are same as Example 1.
Embodiment 9
The present embodiment provides a kind of secondary cell, wherein cathode uses copper-tin alloy, other are same as Example 1.
Embodiment 10
The present embodiment provides a kind of secondary cell, wherein cathode uses utter misery aluminium foil, other are same as Example 1.
The secondary cell preparation process of embodiment 7-10 and embodiment 1 is different except negative material, other all steps and makes Material is all identical, at the same under the conditions of the 2C charge and discharge of the battery of embodiment 7-10 specific discharge capacity, energy density, with And cyclical stability is tested, and is compared with the performance of the embodiment of the present invention 1, referring specifically to table 2.
The performance parameter table of the secondary cell of 2 embodiment 7-10 of table
From table 2 it can be seen that when cathode selects metal foil the secondary cell that is prepared be respectively provided with good specific capacity, Energy density and cycle the number of turns, and select the metal foil containing aluminium be prepared the specific capacity of secondary cell, energy density and It is more preferable to recycle the number of turns.Meanwhile battery is significantly reduced as negative current collector and negative electrode active material using metal foil Weight and volume reduces preparation process.
Embodiment 11
The present embodiment provides a kind of secondary cell, wherein electrolyte lithium salt uses bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI), other are same as Example 1.
Embodiment 12
The present embodiment provides a kind of secondary cell, wherein electrolyte lithium salt uses LiBF4 (LiBF4), other and reality It is identical to apply example 1.
Embodiment 13
The present embodiment provides a kind of secondary cell, wherein electrolyte lithium salt uses trifluoromethayl sulfonic acid lithium (LiCF3SO3), He is same as Example 1.
Embodiment 14
The present embodiment provides a kind of secondary cell, wherein electrolyte lithium salt uses lithium perchlorate (LiClO4), other and reality It is identical to apply example 1.
The secondary cell preparation process of embodiment 11-14 and embodiment 1 except in electrolyte lithium salts it is different, other all steps And the material used is all identical, while close to specific discharge capacity, the energy under the conditions of the 2C charge and discharge of the battery of embodiment 11-14 Degree and cyclical stability are tested, and be compared with the performance of the embodiment of the present invention 1, referring specifically to table 3.
The performance parameter table of the secondary cell of 3 embodiment 11-14 of table
From table 3 it can be seen that whens lithium salts selects lithium hexafluoro phosphate, LiBF4 etc. in electrolyte, be prepared two Primary cell has better specific capacity, energy density and the cycle number of turns.
Embodiment 15
The present embodiment provides a kind of secondary cells, and organic solvent is methyl ethyl carbonate (EMC) and carbonic acid wherein in electrolyte Vinyl acetate (EC), the two volume are 1:1, other are same as Example 1.
Embodiment 16
The present embodiment provides a kind of secondary cells, and organic solvent is propene carbonate (PC) and carbonic acid first wherein in electrolyte Ethyl ester (EMC), the two volume are 4:6, other are same as Example 1.
Embodiment 17
The present embodiment provides a kind of secondary cells, and organic solvent is diethyl carbonate (DEC) and carbonic acid wherein in electrolyte Vinyl acetate (EC), the two volume are 1:1, other are same as Example 1.
Embodiment 18
The present embodiment provides a kind of secondary cells, and organic solvent is ethylene carbonate (EC), carbonic acid two wherein in electrolyte Methyl esters (DMC), methyl ethyl carbonate (EMC), three's volume are 1:1:1, other are same as Example 1.
The secondary cell preparation process of embodiment 15-18 and embodiment 1 is different except electrolyte solvent, other all steps and The material used is all identical, while close to specific discharge capacity, the energy under the conditions of the 2C charge and discharge of the battery of embodiment 15-18 Degree and cyclical stability are tested, and be compared with the performance of the embodiment of the present invention 1, referring specifically to table 4.
The performance parameter table of the secondary cell of 4 embodiment 15-18 of table
From table 4, it can be seen that when solvent selects methyl ethyl carbonate in electrolyte, the secondary cell being prepared has more preferably Specific capacity, energy density and cycle the number of turns.
Embodiment 19
The present embodiment provides a concentration of 0.5mol/L of a kind of secondary cell, wherein electrolyte lithium salt, other and embodiment 1 It is identical.
Embodiment 20
The present embodiment provides a concentration of 1mol/L of a kind of secondary cell, wherein electrolyte lithium salt, other and 1 phase of embodiment Together.
Embodiment 21
The present embodiment provides a concentration of 2mol/L of a kind of secondary cell, wherein electrolyte lithium salt, other and 1 phase of embodiment Together.
Embodiment 22
The present embodiment provides a concentration of 3mol/L of a kind of secondary cell, wherein electrolyte lithium salt, other and 1 phase of embodiment Together.
The secondary cell preparation process of embodiment 19-22 and embodiment 1 is used as using lithium hexafluoro phosphate (LiPF6) to be electrolysed Lithium salts in matter, except the selection concentration of lithium salts is different, other all steps and the material used are all identical, while to embodiment Specific discharge capacity, energy density and cyclical stability under the conditions of the 2C charge and discharge of the battery of 19-22 are tested, and with The performance of the embodiment of the present invention 1 is compared, referring specifically to table 5.
The performance parameter table of the secondary cell of 5 embodiment 19-22 of table
As can be seen from Table 5, when electrolyte lithium salinity is more than 1mol/L, the secondary cell being prepared has well Specific capacity and energy density, as a concentration of 4mol/L of electrolyte lithium salt, the secondary cell being prepared has better specific volume Amount, energy density and the cycle number of turns.
The present embodiments relate to secondary cell form be not limited to button cell, can be also designed to according to core component The forms such as soft-package battery, cylindrical battery.The anode of secondary battery active constituent of the embodiment of the present invention is to live with reversible embedding de- lithium The organic material of property or reversible Doped anions activity, and without negative electrode active material in battery system, thus can significantly reduce Battery is conducted oneself with dignity and manufacturing cost, battery energy density is promoted, while the battery has excellent stable circulation performance, in secondary electricity Pond field has broad application prospects.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of secondary cell, which is characterized in that including anode, cathode and be set between the anode and the cathode Diaphragm and electrolyte, the anode includes plus plate current-collecting body and the positive electrode active materials that are arranged on the plus plate current-collecting body Layer, the anode active material layer include positive electrode active materials, and the positive electrode active materials include having reversible embedding de- lithium activity Or the organic material of reversible Doped anions activity；The cathode includes metal foil, and the metal foil is simultaneously as cathode Collector and negative electrode active material.
2. secondary cell as described in claim 1, which is characterized in that the positive electrode active materials include conducting high polymers It is one or more in object, sulfur-containing compound, compound oxygen radical of nitrogen, oxygen-containing conjugated compound.
3. secondary cell as claimed in claim 2, which is characterized in that the conducting high polymers object includes polypyrrole, gathers It is aniline, poly- to one or more in benzene, polyacetylene, polythiophene, the sulfur-containing compound include Allifridin, One or more in diallyl trisulfide, diallyl disulfide, the compound oxygen radical of nitrogen includes 2,2,6,6- Tetramethyl piperidine-nitrogen-at least one of oxide and its polymer, it is described it is oxygen-containing conjugation organic matter include quinones, It is one or more in acid anhydrides containing conjugated structure.
4. secondary cell as described in claim 1, which is characterized in that the anode active material layer further includes conductive agent and glues Agent is tied, the conductive agent is included in conductive black, conductive carbon ball, electrically conductive graphite, carbon nanotube, conductive carbon fibre, graphene It is one or more, the binding agent include Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, It is one or more in polyolefins.
5. secondary cell as claimed in claim 4, which is characterized in that in the anode active material layer, the positive-active The mass content of material is 60-90%, and the mass content of the conductive agent is 2-30%, and the mass content of the binding agent is 3- 10%.
6. secondary cell as described in claim 1, which is characterized in that the material of the metal foil include aluminium, copper, iron, tin, Any one in zinc, nickel, titanium, manganese or the alloy containing at least one above-mentioned metallic element contain at least one above-mentioned gold Belonging to the composite material of element, the material of the plus plate current-collecting body includes any one in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese, Or the alloy containing at least one above-mentioned metallic element or the composite material containing at least one above-mentioned metallic element.
7. secondary cell as described in claim 1, which is characterized in that the electrolyte includes lithium salts and solvent, the solvent Including one or more in esters, sulfone class or ether organic solvent.
8. secondary cell as claimed in claim 7, which is characterized in that the electrolyte further includes additive, the additive Including one or more in esters, sulfone class, ethers, nitrile and olefines organic additive, the additive is in the electrolysis Mass fraction in liquid is 0.1%-20%.
9. secondary cell as described in claim 1, which is characterized in that the diaphragm is the porous polymer film or exhausted of insulation The inorganic porous film of edge.
10. a kind of preparation method of secondary cell, which is characterized in that including：
Plus plate current-collecting body is provided, anode active material layer is prepared on the plus plate current-collecting body, is cut into after dry, compacting required Size obtains anode, and the anode active material layer includes positive electrode active materials, and the positive electrode active materials include having reversible The organic material of embedding de- lithium activity or reversible Doped anions activity；
Metal foil is cut into required size, after surface clean, drying, obtains cathode, the metal foil is made simultaneously For negative current collector and negative electrode active material；
Electrolyte and diaphragm are provided, under inert gas or water-less environment, by the cathode, diaphragm, anode successively Close stack, Adding in the electrolyte makes the diaphragm complete wetting, and above-mentioned stacking portion then is encapsulated into battery case, obtains secondary electricity Pond.
CN201711421169.4A 2017-12-25 2017-12-25 A kind of secondary cell and preparation method thereof Pending CN108199044A (en)

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CN109546222A (en) * 2018-11-28 2019-03-29 深圳中科瑞能实业有限公司 Aluminum honeycomb energy storage device electrolyte, aluminum honeycomb energy storage device and preparation method thereof
CN109560339A (en) * 2018-11-27 2019-04-02 中国科学院青岛生物能源与过程研究所 A kind of pre- embedding anion method and full battery
CN109817980A (en) * 2019-03-21 2019-05-28 合肥华思***有限公司 The preparation method of secondary battery electrode active materials and secondary cell containing the material
CN110299509A (en) * 2019-05-16 2019-10-01 同济大学 Lithium ion battery negative electrode, preparation method and lithium ion secondary battery

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CN103765657A (en) * 2011-06-29 2014-04-30 日东电工株式会社 Nonaqueous-electrolyte secondary battery and positive-electrode sheet therefor
CN106340651A (en) * 2015-11-18 2017-01-18 中国科学院深圳先进技术研究院 Secondary battery and preparing method thereof

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Publication number Priority date Publication date Assignee Title
CN103765657A (en) * 2011-06-29 2014-04-30 日东电工株式会社 Nonaqueous-electrolyte secondary battery and positive-electrode sheet therefor
CN106340651A (en) * 2015-11-18 2017-01-18 中国科学院深圳先进技术研究院 Secondary battery and preparing method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109560339A (en) * 2018-11-27 2019-04-02 中国科学院青岛生物能源与过程研究所 A kind of pre- embedding anion method and full battery
CN109560339B (en) * 2018-11-27 2021-12-03 中国科学院青岛生物能源与过程研究所 Method for pre-embedding anions and full battery
CN109546222A (en) * 2018-11-28 2019-03-29 深圳中科瑞能实业有限公司 Aluminum honeycomb energy storage device electrolyte, aluminum honeycomb energy storage device and preparation method thereof
CN109817980A (en) * 2019-03-21 2019-05-28 合肥华思***有限公司 The preparation method of secondary battery electrode active materials and secondary cell containing the material
CN110299509A (en) * 2019-05-16 2019-10-01 同济大学 Lithium ion battery negative electrode, preparation method and lithium ion secondary battery

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Application publication date: 20180622