CN110299513A - A kind of preparation method, parent's lithium cathode and the lithium battery of parent's lithium cathode - Google Patents

A kind of preparation method, parent's lithium cathode and the lithium battery of parent's lithium cathode Download PDF

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CN110299513A
CN110299513A CN201910558152.6A CN201910558152A CN110299513A CN 110299513 A CN110299513 A CN 110299513A CN 201910558152 A CN201910558152 A CN 201910558152A CN 110299513 A CN110299513 A CN 110299513A
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lithium
cathode
close
parent
preparation
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CN110299513B (en
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王接喜
柳天成
胡启阳
李新海
谭磊
颜果春
王志兴
郭华军
彭文杰
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Central South University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The present invention provides a kind of preparation method of close lithium cathode, close lithium cathode and lithium battery, (1) is by MXNO3It is dissolved in organic solvent mixed liquor and M is madexNO3Solution, wherein M is the low metal of metal activity ratio Li；(2) close lithium cathode is prepared: by above-mentioned MxNO3Solution is added dropwise to lithium piece surface, reacts, and generates M or M/Li alloy, obtains the M/Li combination electrode of close lithium, evaporate solvent, the LiNO3It is deposited on the surface of the combination electrode.The purpose is to optimize the preparation method of close lithium matrix, close lithium cathode can not only be obtained using this method, while LiNO can be obtained3.Parent's lithium cathode can not only adjust lithium forming core, reduce overpotential.And lithium ion distribution can be homogenized, realize uniform lithium deposition.

Description

A kind of preparation method, parent's lithium cathode and the lithium battery of parent's lithium cathode
Technical field
The present invention relates to Physical Chemistry of Metallurgy field, in particular to a kind of the preparation method and application of close lithium cathode.
Background technique
With the continuous development of electric car and portable device, high energy density cells system demand is increasingly increased Greatly.Conventional lithium ion battery is unable to satisfy the demand of high-energy density energy storage device due to lower capacity and energy density.Separately On the one hand, lithium metal has high theoretical specific capacity (3860mAh/g), minimum oxidation-reduction potential (- 3.04V vs SHE). Especially in terms of providing power for electric car, lithium metal battery shows apparent advantage in cruising ability.Lithium metal with Transition metal oxide matches its theoretical energy density up to 440Wh/Kg, reachable with elemental sulfur matching theory energy density 650Wh/Kg, the energy density compared with lithium ion battery 300Wh/Kg are with the obvious advantage.
But lithium an- ode is very active, is easy that side reaction occurs with electrolyte, accelerates electrolyte depletion rate.And And lithium metal tends to two-dimensional linear growth during the deposition process, generates Li dendrite.One side dendrite is easy to fall off, and becomes " dead Lithium ", " dead lithium " can not participate in electrochemical reaction, lead to active material irreversible loss.On the other hand, dendrite is constantly grown, and is held Diaphragm is easily pierced through, serious security risk is generated.In addition, lithium metal volume change during deposition/disengaging be it is infinitely great, It will lead to the swollen packet of battery.
In order to solve problem above, patent CN 106252722A is prepared for a kind of additive, is able to suppress the growth of dendrite The method that University of Maryland Hu Liangbing uses Joule heating plates the silver of one layer of close lithium on carbon nano-fiber.Due to close lithium Property matrix can reduce lithium forming core overpotential, and the method achieve lithium uniform deposition (Ultrafine Silver Nanoparticles for Seeded Lithium Deposition toward Stable Lithium Metal Anode.Advanced materials 2017,29(38))。
The close lithium matrix of this current research stablizes lithium deposition for us and provides thinking.But it is most of at present close Lithium matrix is used in combination with 3D collector, and it reduce the capacity of entire battery system and energy densities.In order to sufficiently sharp With the high specific capacity of lithium metal, lithium metal is preferably allowed to keep most original state, such as lithium piece.Furthermore most of parent's lithium base Matter preparation flow is complicated, the high requirements on the equipment, and major part can not be realized at normal temperature.
Summary of the invention
The present invention provides a kind of close lithium cathode of lithium preparation methods, and the purpose is to optimize the preparation side of close lithium matrix Method is distributed by adjusting lithium forming core and homogenization lithium ion, realizes uniform lithium deposition, extend the lithium metal battery service life, this Outside, close lithium cathode can not only be obtained using this method, while LiNO can be obtained3, lithium nitrate adds as lithium metal battery Add agent, it being capable of stable metal cathode of lithium.
On the one hand, the present invention provides a kind of preparation method of close lithium cathode, include the following steps:
(1) by MXNO3It is dissolved in organic solvent mixed liquor and M is madexNO3Solution, wherein M is that metal activity ratio Li is low Metal, the organic solvent mixed liquor includes nitrogenous organic solvent；
(2) close lithium cathode is prepared: by above-mentioned MxNO3Solution is added dropwise to lithium piece surface, reacts, and generates M or M/Li and closes Gold and LiNO3, wherein generating M or M/Li by the MXNO3Concentration and dropwise addition amount influence, M the or M/Li alloy covers The M/Li combination electrode that the surface in the lithium piece forms close lithium is covered, solvent, the LiNO are evaporated3It is deposited on described compound The surface of electrode obtains the close lithium cathode.It should be noted that the wherein MXNO3Concentration and dropwise addition amount it is different, So that the substance that reaction generates also can be different, that react generation is M simple substance and LiNO3Either M/Li alloy and LiNO3。
Wherein, the M is Ag, Cu, Al, Zn, Fe, Co, Ni, Sn, Au, Pt, one of In or several.
Wherein, the M is Ag or Al or Sn.
Wherein, the nitrogenous organic solvent is N-Methyl pyrrolidone (NMP), dimethylformamide (DMF) and acetonitrile (C2H3N one of) or a variety of.
Wherein, the organic solvent mixed liquor further includes dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), carbonic acid diethyl Ester (DC) is ethylene carbonate (EC), diethyl carbonate (DEC), polycarbonate (PC), tetrahydrofuran (THF), tetraethylene glycol two One of methyl ether, 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME) are a variety of.
Wherein, the MxNO3Concentration range be 0.01mol/L~1mol/L.
Wherein, M in the step (2)xNO3Dripping quantity be 50 μ of μ L~150 L.
On the other hand, the present invention also provides a kind of close lithium cathode, and parent's lithium cathode is using close lithium above-mentioned The preparation method of cathode is prepared.
The present invention also provides a kind of lithium battery, the lithium battery includes the close lithium cathode and anode, the anode Using LiFePO4 (LiFePO4), LiMn2O4 (LiMn2O4), lithium titanate (Li4Ti5O12), lithium nickelate (LiNiO2), nickel cobalt binary (LiNiCoO2), cobalt acid lithium (LiCoO2), nickel-cobalt-manganese ternary (NCM), elemental sulfur, organic sulfur compound or carbon sulfide is prepared.
The present invention also provides a kind of lithium battery, the lithium battery is Symmetrical cells, and the Symmetrical cells include described The anode of close lithium cathode, the Symmetrical cells is identical with cathode.
Present invention has the advantage that
(1) nitrate is dissolved in the organic solvent of N-Methyl pyrrolidone (NMP) by close lithium cathode of the invention first In, the N-Methyl pyrrolidone (NMP) disperses nitrate ion therein, obtains nitrate solution, then will be described Nitrate solution drop reacts to obtain metal M or M/Li alloy and LiNO in lithium piece3, wherein generating M or M/Li by institute State MXNO3Concentration and dropwise addition amount influence, the LiNO3It is deposited on M/Li combination electrode, the reaction product in the present invention LiNO3, can be used as the additional additive of one kind and be reduced into LiN during circulating batteryXOYAnd Li3N, this solid Electrolyte layer is able to suppress the growth of Li dendrite, reduces interface impedance, to stablize lithium deposition, extends the lithium metal battery service life, When the lithium nitrate of generation is washed to remove, battery performance is declined.The work that metal M or M/Li alloy can be deposited as lithium Property site induction lithium deposition.The two acts on stable metal lithium electrode simultaneously, extends lithium metal battery service life, whole process system Standby process is short, simple process, and can carry out at normal temperature.
(3) metal M or the M/Li alloy generated can alleviate dendrite as the active site induction lithium deposition that lithium deposits.
(4) free energy as needed for out-phase forming core is lower, and when lithium piece is when preparing M/Li combination electrode forming core, obstacle is more Small, required energy is lower, and lithium forming core overpotential can be lower, be conducive to lithium metal forming core and subsequent deposition.
(5) M/Li combination electrode adjustable lithium ion distribution, lithium ion can be distributed above it is more uniform, to have Conducive to lithium uniform after electrochemical reduction deposition.
(6) the close lithium cathode prepared when matching with other positive electrodes, can be realized the long-life circulation of battery.
(7) organic solvent mixed liquor includes nitrogenous organic solvent, and the nitrogenous organic solvent is N- methylpyrrole Alkanone (NMP), dimethylformamide (DMF) and acetonitrile (C2H3N one of) or a variety of, the nitrogenous organic solvent is main It is so that nitrate dissolution is prepared into nitrate solution in organic solvent in order to disperse nitrate ion, reaction obtains product LiNO3.Meanwhile organic solvent mixed liquor of the invention further includes dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), tetrem two The organic solvent of the esters such as diethylene glycol dimethyl ether or ethers, and wherein the content of the organic solvent of the esters or ethers be higher than it is described Nitrogenous class organic solvent, because the organic solvent of esters or ethers is easier to evaporate relative to nitrogenous organic solvent, in step (2) LiNO can be made effectively by the organic solvent evaporation in3It is deposited on M/Li combination electrode surface, therefore in the present invention Organic solvent be the organic solvent mixed liquor for including nitrogenous organic solvent.
Detailed description of the invention
(a) is the lithium ion distribution situation of unmodified lithium piece in Fig. 1；
(b) the lithium ion distribution situation of close lithium combination electrode is provided for the embodiment of the present invention；
It (c) is the forming core overpotential situation in unmodified lithium piece as cathode；
(d) forming core overpotential situation of the close lithium combination electrode as cathode is provided for the embodiment of the present invention；
Fig. 2 is the circulating ring number and coulombic efficiency figure of the lithium battery in the embodiment of the present invention 1；
Fig. 3 is the circulation figure of the lithium battery in the embodiment of the present invention 2；
Fig. 4 is that close lithium Ag/Li combination electrode Symmetrical cells voltage curve (retains the LiNO generated3)；
Fig. 5 is that close lithium Ag/Li combination electrode Symmetrical cells voltage curve (washes away the LiNO of generation3)。
Fig. 6 is the circulating ring number and coulombic efficiency figure of the lithium battery in the embodiment of the present invention 5.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with embodiment and more comprehensively, is meticulously described, but this The protection scope of invention is not limited to specific embodiment.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
On the one hand, the preparation method for present embodiments providing a kind of close lithium cathode, includes the following steps:
(1) by AgNO3It is dissolved in the organic solvent mixed liquor containing N-Methyl pyrrolidone (NMP) and AgNO is made3Solution, The organic solvent further includes 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME)；Wherein 1,3- dioxolanes (DOL)/ Glycol dimethyl ether (DME) volume ratio is 1:1, and N-Methyl pyrrolidone (NMP) volume fraction is 20%, AgNO3Solution it is dense Degree is 0.01mol/L；
(2) close lithium cathode is prepared: by above-mentioned AgNO3150 μ L of solution is added dropwise to lithium piece surface, reacts, and generates Ag And LiNO3, the surface that the Ag is covered on the lithium piece forms the Ag/Li combination electrode of close lithium, evaporates solvent, described LiNO3It is deposited on the surface of the combination electrode, obtains the close lithium cathode.
Above-mentioned N-Methyl pyrrolidone (NMP) is nitrogenous organic solvent, which can be by nitrate anion Ion is dispersed in organic solvent mixed liquor, to make AgNO3It is dissolved in the organic solvent mixed liquor and obtains AgNO3Solution. The organic solvent mixed liquor further includes 1,3-dioxolane (DOL) and glycol dimethyl ether (DME), and 1, the 3- dioxy penta Ring (DOL) and glycol dimethyl ether (DME) volume ratio are 1:1, and N-Methyl pyrrolidone (NMP) volume fraction is 20%, 1,3- Dioxolanes (DOL) and glycol dimethyl ether (DME) obtain volume fraction much larger than the N-Methyl pyrrolidone (NMP) volume point Number is primarily due to 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME) more holds relative to N-Methyl pyrrolidone (NMP) Easily evaporation, makes the LiNO3It is deposited on the surface of the combination electrode, obtains the close lithium cathode.
On the other hand, the present embodiment additionally provides a kind of close lithium cathode, and parent's lithium cathode is using close lithium above-mentioned The preparation method of cathode is prepared.
The present embodiment additionally provides a kind of lithium battery, and the lithium battery includes that close lithium Ag/Li combination electrode above-mentioned is Cathode, anode, diaphragm and electrolyte solution, the preparation method of the anode comprising steps of
(1) by LiFePO4 (LiFePO4), conductive black (Super P), Kynoar (PVDF) in mass ratio 80: 10:10 grinding uniformly, with N-Methyl pyrrolidone (NMP) for dispersing agent, is obtained in blender with the speed stirring 1h of 600rpm To slurry；
(2) the obtained slurry is uniformly coated on the carbon containing aluminium foil of collector, is then done in 120 DEG C of vacuum tank Dry 24 hours, obtain the anode.
Further, the diaphragm is Celgard2400.
Further, the electrolyte solution includes 1mol/L lithium hexafluoro phosphate (LiPF6) electrolytic salt and electrolysis Liquid solvent, the electrolyte solvent are the mixed liquor of ethyl carbonate (EC) electrolyte and diethyl carbonate (DEC) electrolyte.
(a) is the lithium ion distribution situation of unmodified lithium piece in Fig. 1, and it is multiple (b) to provide close lithium for the embodiment of the present invention The lithium ion distribution situation of composite electrode.It is smaller to scheme (b) interfacial contact angle, shows that lithium ion can be on Ag/Li combination electrode uniformly Distribution, this is conducive to the uniform deposition of lithium in further battery cyclic process.
Fig. 2 is that the lithium battery that embodiment 1 provides carries out constant current charge-discharge, blanking voltage 2.2-4.2V with 1C multiplying power.It can Circulation 200 times, average coulombic efficiencies 99.9%.
Embodiment 2:
On the one hand, the preparation method for present embodiments providing a kind of close lithium cathode, includes the following steps:
(1) by AgNO3It is dissolved in the organic solvent mixed liquor containing N-Methyl pyrrolidone (NMP) and AgNO is made3Solution, The organic solvent further includes ethylene carbonate (EC), and N-Methyl pyrrolidone (NMP) volume fraction is 40%, wherein AgNO3The concentration of solution is 1mol/L；
(2) close lithium cathode is prepared: by above-mentioned AgNO350 μ L of solution is added dropwise to lithium piece surface, reacts, and generates Ag/ Li alloy and LiNO3, the surface that the Ag/Li alloy is covered on the lithium piece forms the Ag/Li combination electrode of close lithium, evaporates Fall solvent, the LiNO3It is deposited on the surface of the combination electrode, obtains the close lithium cathode.
On the other hand, the present embodiment additionally provides a kind of close lithium cathode, and parent's lithium cathode is using close lithium above-mentioned The preparation method of cathode is prepared.
The present embodiment additionally provides a kind of lithium battery, and the lithium battery includes that close lithium Ag/Li combination electrode above-mentioned is Cathode, anode, diaphragm and electrolyte solution, the preparation method of the anode comprising steps of
(1) by lithium titanate (Li4Ti5O12), conductive black (Super P), Kynoar (PVDF) in mass ratio 80: 10:10 grinding uniformly, with N-Methyl pyrrolidone (NMP) for dispersing agent, is stirred in blender with the speed of 500rpm 30min, the slurry that will be obtained；
It is (2) on a current collector by the obtained slurry even spread, then 24 hours dry in 80 DEG C of vacuum tank, As anode.
It is described further, the diaphragm be Celgard 2400.
Further, the electrolyte solution includes 1mol/L lithium hexafluoro phosphate (LiPF6) electrolytic salt and electrolysis Liquid solvent, the electrolyte solvent are the mixed liquor of ethyl carbonate (EC) electrolyte and diethyl carbonate (DEC) electrolyte.
Fig. 3 is lithium battery provided in this embodiment with 1C multiplying power progress constant current charge-discharge, is recycled more than 800 times.
Embodiment 3:
On the one hand, the preparation method for present embodiments providing a kind of close lithium cathode, includes the following steps:
(1) by AgNO3It is dissolved in the organic solvent mixed liquor containing N-Methyl pyrrolidone (NMP) and AgNO is made3Solution, The organic solvent further includes dimethyl carbonate (DMC), and N-Methyl pyrrolidone (NMP) volume fraction is 5%, wherein AgNO3The concentration of solution is 0.05mol/L；
(2) it prepares close lithium cathode: taking above-mentioned AgNO3100 μ L of solution is added dropwise to lithium piece surface, reacts, and generates Ag And LiNO3, the surface that the Ag is covered on the lithium piece forms the Ag/Li combination electrode of close lithium, evaporates solvent, described LiNO3It is deposited on the surface of the combination electrode, obtains the close lithium cathode.
On the other hand, the present embodiment additionally provides a kind of close lithium cathode, and parent's lithium cathode is using close lithium above-mentioned The preparation method of cathode is prepared.
The present invention also provides a kind of lithium battery, the lithium battery the preparation method comprises the following steps: by close lithium Ag/ obtained above Li combination electrode is assembled into 2032 type Symmetrical cells, and the Symmetrical cells refer to cathode and anode is close lithium Ag/Li multiple Glycol dimethyl ether (DME) and 1,3-dioxolane (DOL) that electrolyte is 50 microlitres, the ethylene glycol two is added in composite electrode The volume ratio of methyl ether (DME) and 1,3-dioxolane (DOL) is 1:1, and double fluoroform sulphonyl that electrolytic salt is 1mol/L are sub- Amine lithium (LiTFSI).
Fixed each cycle charge discharge capacitance is 1mAh/cm2, current density 1mA/cm2, Symmetrical cells are in conditions above Lower carry out charge-discharge test can stablize 1000 circle of circulation, and average voltage polarization is 45mV, and overpotential is highly stable, such as Fig. 4 It is shown.
Embodiment 4
On the basis of above-described embodiment 3, under same test condition, by the LiNO of generation3Washing removes, Symmetrical cells Can relatively it is stable circulation 500 circle, voltage polarizing 60mV, as shown in Figure 5.Voltage fluctuation and voltage polarizing value are compared with reservation The group of lithium nitrate is slightly larger.This it is demonstrated experimentally that silver-colored lithium combination electrode and generation lithium nitrate collective effect stable metal lithium Electrode.
Embodiment 5
On the one hand, the preparation method for present embodiments providing a kind of close lithium cathode, includes the following steps:
(1) by Al (NO3)3It is dissolved in the organic solvent mixed liquor containing dimethylformamide (DMF) and Al (NO is made3)3It is molten Liquid, the organic solvent further include methyl ethyl carbonate (EMC), the dimethylformamide (DMF) that volume fraction is 30%, Al (NO3)3The concentration of solution is 0.2mol/L；
(2) close lithium cathode is prepared: by above-mentioned Al (NO3)3100 μ L of solution is added dropwise to lithium piece surface, reacts, and generates Al and LiNO3, the surface that the Al is covered on the lithium piece forms the Al/Li combination electrode of close lithium, evaporates solvent, described LiNO3It is deposited on the surface of the combination electrode, obtains the close lithium cathode.
On the other hand, the present embodiment additionally provides a kind of close lithium cathode, and parent's lithium cathode is using close lithium above-mentioned The preparation method of cathode is prepared.
The present embodiment additionally provides a kind of lithium battery, and the lithium battery includes that close lithium Al/Li combination electrode above-mentioned is Cathode, anode, diaphragm and electrolyte solution, the preparation method of the anode comprising steps of
(1) by LiFePO4 (LiFePO4), conductive black (Super P), Kynoar (PVDF) in mass ratio 80: 10:10 grinding uniformly, with N-Methyl pyrrolidone (NMP) for dispersing agent, is obtained in blender with the speed stirring 1h of 600rpm To slurry；
(2) the obtained slurry is uniformly coated on the carbon containing aluminium foil of collector, is then done in 120 DEG C of vacuum tank Dry 24 hours, obtain the anode.
Further, the diaphragm is Celgard2400.
Further, the electrolyte solution includes electrolytic salt and the electrolysis of 1mol/L lithium hexafluoro phosphate (LiPF6) Liquid solvent, the electrolyte solvent are the mixed liquor of ethyl carbonate (EC) electrolyte and diethyl carbonate (DEC) electrolyte.
Fig. 6 is that the lithium battery that embodiment 1 provides carries out constant current charge-discharge, blanking voltage 2.2-4.2V with 0.5C multiplying power. It is more than 400 times recyclable, average coulombic efficiencies 99.8%.
Embodiment 6
On the one hand, the preparation method for present embodiments providing a kind of close lithium cathode, includes the following steps:
(1) by Sn (NO3)4It is dissolved in (the C containing acetonitrile2H3N Sn (NO is made in organic solvent mixed liquor)3)4Solution, it is described Organic solvent further includes glycol dimethyl ether (DME) and 1,3- dioxolanes (DOL), the acetonitrile (C2H3N) volume fraction is 10%, wherein Sn (NO3)4The concentration of solution is 0.15mol/L；
(2) it prepares close lithium cathode: taking above-mentioned Sn (NO3)4150 μ L of solution is added dropwise to lithium piece surface, reacts, and generates Sn and LiNO3, the surface that the Sn is covered on the lithium piece forms the Sn/Li combination electrode of close lithium, evaporates solvent, described LiNO3It is deposited on the surface of the combination electrode, obtains the close lithium cathode.
On the other hand, the present embodiment additionally provides a kind of close lithium cathode, and parent's lithium cathode is using close lithium above-mentioned The preparation method of cathode is prepared.
The present invention also provides a kind of lithium battery, the lithium battery the preparation method comprises the following steps: by close lithium Sn/ obtained above Li combination electrode is assembled into 2032 type Symmetrical cells, and the Symmetrical cells refer to cathode and anode is close lithium Sn/Li multiple Glycol dimethyl ether (DME) and 1,3-dioxolane (DOL) that electrolyte is 50 microlitres, the ethylene glycol two is added in composite electrode The volume ratio of methyl ether (DME) and 1,3-dioxolane (DOL) is 1:1, and double fluoroform sulphonyl that electrolytic salt is 1mol/L are sub- Amine lithium (LiTFSI).
Fixed each cycle charge discharge capacitance is 1mAh/cm2, current density 2mA/cm2, Symmetrical cells are in conditions above Lower carry out charge-discharge test can stablize 400 circle of circulation, and average voltage polarization is 55mV, and overpotential is highly stable.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of parent's lithium cathode, which comprises the steps of:
(1) by MXNO3It is dissolved in organic solvent mixed liquor and M is madexNO3Solution, wherein M is the low gold of metal activity ratio Li Belong to, the organic solvent mixed liquor includes nitrogenous organic solvent；
(2) close lithium cathode is prepared: by above-mentioned MxNO3Solution is added dropwise to lithium piece surface, reacts, generate M or M/Li alloy and LiNO3, the surface that the M or M/Li alloy is covered on the lithium piece forms the M/Li combination electrode of close lithium, evaporates solvent, The LiNO3It is deposited on the surface of the combination electrode, obtains the close lithium cathode.
2. the preparation method of parent's lithium cathode according to claim 1, which is characterized in that the M is Ag, Cu, Al, Zn, One of Fe, Co, Ni, Sn, Au, Pt, In are several.
3. the preparation method of parent's lithium cathode according to claim 2, which is characterized in that the M is Ag or Al or Sn.
4. the preparation method of parent's lithium cathode according to claim 1, which is characterized in that the nitrogenous organic solvent is N-Methyl pyrrolidone (NMP), dimethylformamide (DMF) and acetonitrile (C2H3N one of) or a variety of.
5. the preparation method of parent's lithium cathode according to claim 4, which is characterized in that organic in the step (1) Solvent mixed liquor further includes dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DC), is ethylene carbonate (EC), diethyl carbonate (DEC), polycarbonate (PC), tetrahydrofuran (THF), tetraethyleneglycol dimethyl ether, 1,3- dioxolanes (DOL) and one of glycol dimethyl ether (DME) or a variety of.
6. the preparation method of parent's lithium cathode according to claim 1, which is characterized in that the MxNO3Concentration range be 0.01mol/L~1mol/L.
7. the preparation method of parent's lithium cathode according to claim 1, which is characterized in that M in the step (2)xNO3's Dripping quantity is 50 μ of μ L~150 L.
8. a kind of parent's lithium cathode, which is characterized in that parent's lithium cathode is used such as any one of claim 1~7 The preparation method of close lithium cathode is prepared.
9. a kind of lithium battery, which is characterized in that the lithium battery includes close lithium cathode and anode as claimed in claim 8, The anode uses LiFePO4 (LiFePO4), LiMn2O4 (LiMn2O4), lithium titanate (Li4Ti5O12), lithium nickelate (LiNiO2)、 Nickel cobalt binary (LiNiCoO2), cobalt acid lithium (LiCoO2), nickel-cobalt-manganese ternary (NCM), elemental sulfur, organic sulfur compound or carbon sulfide It is prepared.
10. a kind of lithium battery, which is characterized in that the lithium battery is Symmetrical cells, and the Symmetrical cells include such as claim 8 The anode of the close lithium cathode, the Symmetrical cells is identical with cathode.
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