CN106384808A - Lithium ion battery positive electrode sheet, preparation method of lithium ion battery positive electrode sheet, and lithium ion battery - Google Patents

Lithium ion battery positive electrode sheet, preparation method of lithium ion battery positive electrode sheet, and lithium ion battery Download PDF

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Publication number
CN106384808A
CN106384808A CN201611074710.4A CN201611074710A CN106384808A CN 106384808 A CN106384808 A CN 106384808A CN 201611074710 A CN201611074710 A CN 201611074710A CN 106384808 A CN106384808 A CN 106384808A
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lithium
ion battery
layer
positive
binding agent
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CN106384808B (en
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玉正日
冷陈伟
施汉议
梁世硕
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SHENZHEN 3SUN ELECTRONICS Co Ltd
Hunan Three Xun Amperex Technology Ltd
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SHENZHEN 3SUN ELECTRONICS Co Ltd
Hunan Three Xun Amperex Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/139—Processes of manufacture
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

In order to solve the problems of capacity loss of the existing lithium ion secondary battery in the SEI film forming process and harsh operation requirements and poor lithium supplementing effect of the existing lithium supplementing mode, the invention provides a lithium ion battery positive electrode sheet, which comprises a first current collector, a lithium supplementing layer and a positive electrode active layer, wherein the lithium supplementing layer is positioned between the positive electrode active layer and the first current collector; the lithium supplementing layer also comprises reducing lithium compounds; the reducing lithium compounds comprise one or more of L-lithium ascorbate, D-lithium erythorbate, lithium pyrosulfite, lithium sulfite and lithium phytate. Meanwhile, the invention also discloses a preparation method of the positive electrode sheet and a lithium ion battery using the positive electrode sheet. By using the technical scheme, the lithium loss of the positive electrode active layer in the first charging and discharging process can be reduced; the energy density of the battery is increased.

Description

A kind of based lithium-ion battery positive plate and preparation method thereof, lithium ion battery
Technical field
The invention belongs to technical field of lithium ion is and in particular to a kind of based lithium-ion battery positive plate and its preparation side Method, lithium ion battery.
Background technology
Lithium rechargeable battery has the features such as high-energy-density, high circulation life-span, low self-discharge, from the commercialization nineties with Come, always in mobile phone, panel computer, the consumer electronics product such as portable power source obtains and widely applies.In recent years, with air Ambient environment goes from bad to worse, the continuous improvement to environmental consciousness for the people, and lithium rechargeable battery also gradually in automobile, lead by energy storage etc. Domain obtains extensively applies.
Normally, as the both positive and negative polarity active material of lithium rechargeable battery, select and reversible can be discharged and be inserted Enter the material of lithium ion.The amount being capable of the lithium ion of reversible deintercalation then characterizes the capacity of battery.It is known that for non-water power For solution matter lithium secondary battery, during battery first charge and discharge, due to forming solid electrolyte (i.e. SEI in negative terminal surface Film), part lithium being lost, because these losses are irreversible, thus directly resulting in the capacitance loss of battery, thus reducing The energy density of battery.To the lithium secondary battery based on graphite system material with carbon element, first charge-discharge efficiency typically 90% about, Then irreversible capacity loss rate is 10% about；To the lithium secondary battery based on alloy material (as silicon, stannum etc.), first charge-discharge Efficiency is lower, and the capacity of loss is higher, and impact becomes apparent from.If during first charge-discharge being reduced, because negative pole is formed SEI film and that a part of capacity of losing, then the energy density of battery can obtain significant raising.
Chinese patent CN1830110 discloses one kind and may include prelithiation or when introducing electrolyte is in battery, lithium occurs The electrode of the host material changed, and provide the lithiation of host material.In the method, lithium metal is stirred with host material, Apply pressure in lithium metal and matrix material mixture, so that host material is contacted with molten lithium metal, be laminated lithium paper tinsel or lithium net To on the electrode comprising host material, or it is laminated lithium metal or net at high temperature on electrode.Form SEI using lithium metal to subtract Less or eliminate irreversible capacity loss produce battery capacity loss.
In addition CN1773762A discloses a kind of lithium rechargeable battery, including the electricity being made up of positive pole, negative pole and barrier film Pole piece assembly, said modules are encapsulated in metal shell together with nonaqueous electrolytic solution, wherein, also place in described metal shell Have lithium metal, this metal can supplement lithium rechargeable battery in charge and discharge process can intercalation/deintercalation lithium ion amount, subtract The irreversible capacity of few battery.
Lithium metal can also be placed directly within electrode, such as CN102916165A discloses a kind of anode plate for lithium ionic cell The method mending lithium, including in an inert atmosphere, by organolithium spray solution or Deca in negative plate surface, makes in organolithium solution Lithium ion be reduced in lithium metal embedded negative plate, negative plate is then dried.
Above thinking is by introducing the lithium metal of activity come capacitance loss during balancing battery first charge-discharge.But It is that lithium is metal the most active, even if still there is very high activity after carrying out stabilizing treatment it is impossible to long-term in atmosphere Stable existence.Therefore in operation, need to carry out in an inert atmosphere, operating environment requires harsh, process equipment requirement Height, is unfavorable for industrialized production.
The method to mend lithium using lithium metal is therefore avoided also gradually to be disclosed.Chinese patent CN103441236A discloses The alternative thinking mending lithium, the method adopts the compound of lithium as mending lithium material, does not change cathode potential, in formation charging When mend lithium material decompose, decompose produce gas can chemical conversion when remove, decompose produce lithium charge when shifted by negative electrode Form SEI film to anode, filled up the lithium loss forming SEI film, reduced the irreversible capacity of battery, improve the circulation of battery Performance.But the voltage that the method is arranged in chemical conversion is higher, and benefit lithium material decomposition electric potential is higher, dividing of electrolyte can be caused Solution, mend lithium material and its catabolite residual that are mixed in active material can be to the active materials of wherein normal removal lithium embedded simultaneously Produce impact and such as improve the internal resistance of cell, reduce battery high rate charge-discharge performance etc., therefore the benefit lithium effect of the method simultaneously Undesirable.Similarly, Chinese patent CN105702961A introduces additive Li5Fe1-xAlxO4, by it in charging formation process In, de- lithium come to realize mend lithium function, but this additive electronic conductivity is low.Be mixed in benefit lithium material in active material and Its catabolite residual can produce impact to the active material of wherein normal removal lithium embedded.Charging process simultaneously, there is oxygen in additive Change and produce oxygen, reduce at oxygen migration to negative pole, and consume part lithium.Mend lithium effect equally undesirable.
Chinese patent CN105702913A introduces the lithium-containing compound that formula is LixA, by it in initial charge process In de- lithium, to compensate the irreversible loss of SEI, but the program also emphasize more than battery discharge blanking voltage 3.0v simultaneously, with Prevent lithium ion from returning in the benefit lithium layer being embedded into positive pole.But in actual application, because the lithiumation thing being added has oxygen Change reduction reversibility, battery when electric discharge, especially heavy-current discharge when, due to the effect of polarization, battery is actual Voltage can often reach below stopping potential, now may occur that lithium ion returns embedded above-mentioned lithiumation thing oxidation product In, therefore weaken benefit lithium effect.
Content of the invention
There is capacitance loss and existing benefit lithium mode in formation SEI membrane process for existing lithium rechargeable battery to operate Require harsh, mend the undesirable problem of lithium effect, the invention provides a kind of based lithium-ion battery positive plate and preparation method thereof, lithium Ion battery.
The technical scheme that present invention solution above-mentioned technical problem is adopted is as follows：
A kind of based lithium-ion battery positive plate is provided, including the first collector, mends lithium layer and positive-active layer；
Described benefit lithium layer is located between described positive-active layer and described first collector；
Reproducibility lithium compound is contained, described reproducibility lithium compound includes L-AA lithium, D- in described benefit lithium layer One of arabo-ascorbic acid lithium, pyrosulfurous acid lithium, lithium sulfite and phytic acid lithium or multiple.
According to the positive plate of the present invention, there is the function of release lithium, lithium secondary battery can be effectively compensated in discharge and recharge During irreversible capacity loss, improve battery energy density.
According to the positive plate of the present invention, it is capable of the reason mend lithium function and is：Positive pole according to the present invention is first Between collector and positive-active layer, lithium layer is mended in setting, comprises reproducibility lithium compound, this reproducibility lithium in described benefit lithium layer Compound has strong reducing property, during initial charge, takes the lead in oxidized, and the portion capacity contributed is compensate for negative pole shape Become the capacitance loss of SEI film, the lithium of generation is then transferred to anode when charging by negative electrode and formed SEI film in anode, fills up Form the lithium needed for SEI film, because described lithiumation thing oxidation reaction is irreversible, the also generation of no oxygen, when electric discharge, Its oxidation product will not be reduced, and with respect to conventional solution, decomposition voltage is low, and there is not lithium returns embedded benefit lithium material layer In, there is not the phenomenon being consumed by oxygen at anode for the lithium yet, therefore more effectively improve the energy density of battery.
According to the positive plate of the present invention, mend lithium layer and be arranged between the first collector and positive-active layer, will not be to positive pole The normal removal lithium embedded of active layer produces impact, so as to make lithium secondary battery still have excellent electrochemistry cycle performance and relatively Low internal resistance., without using active lithium metal, compared with the technique using lithium metal, it is right to reduce for positive pole according to the present invention In the severity of operating environment and operating procedure, according to the present invention just can be prepared under normal conditions using common process Pole.
Further, described positive-active layer includes positive electrode active materials, the first conductive agent and the first binding agent；
Described positive-active layer includes following components by weight percent：80～99.2 parts of positive electrode active materials, the first conductive agent 0.4～ 10 parts, 0.4～10 part of the first binding agent.
Further, described positive electrode active materials include lithium cobalt composite oxide and its modifier, complex Li-Mn-oxide And its modifier, lithium nickel composite oxide and its modifier, LiFePO4 composite oxides and its modifier, lithium manganese phosphate are combined Oxide and its modifier, phosphoric acid vanadium lithium composite oxides and its modifier, many element/transition metals oxidate for lithium and its modifier And one or more of lithium-rich manganese-based many element/transition metals oxidate for lithium and its modifier.
Further, described first conductive agent include acetylene black, conductive carbon black, electrically conductive graphite, carbon fiber, CNT and One or more of Graphene.
Further, described first binding agent include fluorine resin, polyether resin, Cellulose-type binders, rubber-type glue One or more of knot agent, polyacrylate binding agent and polyimides.
Further, described benefit lithium layer also includes the second conductive agent and the second binding agent；
Described benefit lithium layer includes following components by weight percent：10～90 parts of reproducibility lithium compound, the second 5～50 parts of conductive agent, Second 5～40 parts of binding agent.
Further, described benefit lithium layer includes following components by weight percent：30～80 parts of reproducibility lithium compound, the second conductive agent 10～30 parts, the second 10～40 parts of binding agent.
Further, described second conductive agent include acetylene black, conductive carbon black, electrically conductive graphite, carbon fiber, CNT and One or more of Graphene.
Further, described second binding agent include fluorine resin, polyether resin, Cellulose-type binders, rubber-type glue One or more of knot agent, polyacrylate binding agent and polyimides.
Further, the ratio of the described thickness and the thickness of described positive-active layer mending lithium layer is 0.02～0.4.
Further, the ratio of the described thickness and the thickness of described positive-active layer mending lithium layer is 0.04～0.2.
A kind of preparation method of based lithium-ion battery positive plate, comprises the following steps：
Obtain and mend lithium slurry：Reproducibility lithium compound is contained, described reproducibility lithium compound includes in described benefit lithium slurry One of L-AA lithium, D-araboascorbic acid lithium, pyrosulfurous acid lithium, lithium sulfite and phytic acid lithium or multiple.To mend Lithium slurry is coated at least one surface of the first collector, dries to be formed and mends lithium layer；
Obtain positive-active slurry；
Positive-active slurry is coated on the surface mending lithium layer, dries and form positive-active layer.
Further, the described operation obtaining benefit lithium slurry includes：By reproducibility lithium compound, the second conductive agent and second Binding agent is scattered in the first solvent and obtains mending lithium slurry, and described first solvent includes N-Methyl pyrrolidone, N, N- dimethyl Methanamide, DMAC N,N' dimethyl acetamide, N, one of N- diethylformamide, dimethyl sulfoxide, oxolane, water and alcohol Or it is multiple.
A kind of lithium ion battery, including positive plate as above.
According to the lithium ion battery of the present invention, employ above-mentioned positive plate, there is higher energy density, also have simultaneously Preferably cycle performance and big multiplying power discharging property.
Brief description
Fig. 1 is the structural representation of based lithium-ion battery positive plate provided in an embodiment of the present invention.
Reference in Figure of description is as follows：
1st, the first collector；2nd, mend lithium layer；3rd, positive-active layer.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, below in conjunction with Drawings and Examples, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used To explain the present invention, it is not intended to limit the present invention.
Shown in Figure 1, in a preferred embodiment of the invention, disclose a kind of based lithium-ion battery positive plate, including One collector 1, benefit lithium layer 2 and positive-active layer 3；
Described benefit lithium layer 2 is located between described positive-active layer 3 and described first collector 1；
Described benefit lithium layer 2 includes reproducibility lithium compound, and described reproducibility lithium compound includes L-AA lithium, D- One of arabo-ascorbic acid lithium, pyrosulfurous acid lithium, lithium sulfite and phytic acid lithium or multiple.
Described first collector can be conventional plus plate current-collecting body in lithium secondary battery.Specifically, the first described collection Fluid can be aluminium foil, or punching aluminium foil, or the steel band of punching, and those skilled in the art can be selected as needed. In order to improve the described adhesion mended between lithium layer and the first collector, the surface of described first collector can be carried out chemistry or Physical treatment.
The present embodiment arranges benefit lithium layer between the first collector and positive-active layer, comprises to reduce in described benefit lithium layer Property lithium compound, this reproducibility lithium compound has strong reducing property, during initial charge, takes the lead in oxidized, and contribute Portion capacity forms the capacitance loss of SEI film compensate for negative pole, and the lithium of generation then transfers to anode simultaneously when charging by negative electrode Form SEI film in anode, filled up the lithium being formed needed for SEI film, therefore decrease the lithium loss in active material layer, improve The energy density of battery.
On the other hand, it is arranged at mending lithium layer between positive-active layer and the first collector, benefit lithium layer can be prevented effectively from In reproducibility lithium compound impact is produced on the normal removal lithium embedded in positive pole active layer.
Described positive-active layer includes positive electrode active materials, the first conductive agent and the first binding agent；
In the present embodiment, described positive-active layer includes following components by weight percent：80～99.2 parts of positive electrode active materials, One 0.4～10 part of conductive agent, 0.4～10 part of the first binding agent.
In the case of further preferably, for reaching more preferable implementation result, described positive-active layer includes following components by weight percent： 90～-98.8 parts of positive electrode active materials, 0.6～5 part of the first conductive agent, 0.6～5 part of the first binding agent.
Described positive electrode active materials refer to reversibly to deviate from/embed lithium ion, can be field of lithium ion battery Conventional positive active material.Specifically, described positive electrode active materials include lithium cobalt composite oxide and its modifier, lithium manganese are multiple Close oxide and its modifier, lithium nickel composite oxide and its modifier, LiFePO4 composite oxides and its modifier, phosphoric acid Manganese lithium composite xoide and its modifier, phosphoric acid vanadium lithium composite oxides and its modifier, many element/transition metals oxidate for lithium and One or more of its modifier and lithium-rich manganese-based many element/transition metals oxidate for lithium and its modifier.
Wherein, described lithium cobalt composite oxide is specifically as follows LiCoO2.Described lithium nickel composite oxide is specifically as follows LiNiO2.
Described complex Li-Mn-oxide is specifically as follows LiMn2O4、LiMnO2And LiNi0.5Mn1.5O4One of or many Kind.
Described LiFePO4 composite oxides are specifically as follows LiFePO4.
Described lithium manganese phosphate composite oxides are specifically as follows LiMnPO4.
Described phosphoric acid vanadium lithium composite oxides are specifically as follows Li3V2(PO4)3.
Described many element/transition metals oxidate for lithium is specifically as follows the compound shown in Formulas I,
Formulas I:LiMxNyTzO2
In Formulas I, M, N are different with T, respectively Co, Ni, Mn, Al, Mg, Ca, Ti, V, Cr, Fe, Cu, Zn, Sr or Ru, x, Y and z each represents molal quantity, wherein, 0≤x≤1,0≤y≤1,0≤z≤1, and x+y+z=1.
Described lithium-rich manganese-based many element/transition metals oxidate for lithium is specially with the compound shown in Formula Il
Formula II：aLi2MnO3·(1-a)LiMxNyTzO2
In Formula II, M, N are different with T, respectively Co, Ni, Mn, Al, Mg, Ca, Ti, V, Cr, Fe, Cu, Zn, Sr or Ru, X, y and z each represent molal quantity, wherein, 0≤a≤1,0≤x≤1,0≤y≤1,0≤z≤1, and x+y+z=1.
In the present embodiment, increasing by the first conductive agent can increase the monolithic conductive performance of positive-active layer, solve positive pole The not enough problem of active material self-conductive, improves migration rate in positive-active layer for the electronics.
Described first conductive agent is included in acetylene black, conductive carbon black, electrically conductive graphite, carbon fiber, CNT and Graphene One or more.
Described first binding agent is used for making positive electrode active materials and the first conductive agent dispersed and be securely attached to On one collector, described first binding agent includes fluorine resin, polyether resin, Cellulose-type binders, rubber adhesive, gathers One or more of acrylic ester type binding agent and polyimides.Specifically, described first binding agent be polyvinylidene fluoride, Polyvinylidene fluoride-hexafluoropropene, politef, poly(ethylene oxide), poly(propylene oxide), Polyvinylpyrrolidone, cellulose Type binding agent, one of SBR type binding agent, polyacrylate binding agent and polyimides or two or more.
In the present embodiment, described reproducibility lithium compound includes L-AA lithium, D-araboascorbic acid lithium, burnt sulfurous One of sour lithium, lithium sulfite and phytic acid lithium or multiple.Selected reproducibility lithium compound has strong reducing property, first Positive electrode active materials can be compared during charging relatively first oxidized, and contribute portion capacity to be formed on negative plate to compensate The capacitance loss that SEI film leads to, decreases the lithium loss in active material layer, and will not be reduced in discharge process, bright The aobvious energy density that improve battery.
In the present embodiment, described benefit lithium layer also includes the second conductive agent and the second binding agent, by the second conductive agent The electric conductivity mending lithium layer can be effectively improved, improved by the second binding agent viscous between described benefit lithium layer and the first collector Connect performance.
Described benefit lithium layer includes following components by weight percent：10～90 parts of reproducibility lithium compound, the second 5～50 parts of conductive agent, Second 5～40 parts of binding agent.
In the case of further preferably, for reaching more preferable implementation result, described benefit lithium layer includes following components by weight percent：Reduction 30～80 parts of lithium compound of property, the second 10～30 parts of conductive agent, the second 10～-40 parts of binding agent.
Add the second conductive agent of high deal in mending lithium layer, can effectively reduce between benefit lithium layer and the first collector Contact resistance, mend simultaneously and be in close contact between lithium layer and positive-active layer, thus the secondary electricity of lithium of the positive pole using the present invention Pond also has relatively low internal resistance and good big multiplying power discharging property, can effectively solve the problem that positive-active layer is low because of conductive agent content The big problem of contact resistance and the first collector between.
Described second conductive agent effect similar with the first conductive agent, described second conductive agent include acetylene black, conductive carbon black, One or more of electrically conductive graphite, carbon fiber, CNT and Graphene.
Described second binding agent effect is similar with the first binding agent, and described second binding agent includes fluorine resin, polyethers tree One or more of fat, Cellulose-type binders, rubber adhesive, polyacrylate binding agent and polyimides.Tool Body ground, described second binding agent is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropene, politef, polycyclic oxygen second Alkane, poly(propylene oxide), Polyvinylpyrrolidone, Cellulose-type binders, SBR type binding agent, polyacrylate bonding One of agent and polyimides or two or more.
Preferably, described the second binding agent mended in lithium layer is polyvinylidene fluoride-hexafluoropropene, described positive-active material The first binding agent in the bed of material is polyvinylidene fluoride, and now lithium secondary battery has higher energy density, and also has Preferably cycle performance and big multiplying power discharging property.
The ratio of the described thickness and the thickness of described positive-active layer mending lithium layer is 0.02～0.4.
It is furthermore preferred that the ratio of the thickness of the described thickness mending lithium layer and described positive-active layer is 0.04～0.2, enter one Under step preferable case, for reaching more preferable implementation result, the ratio of the thickness of described benefit lithium layer and the thickness of described positive-active layer It is worth for 0.05～0.1.
Another embodiment of the present invention also discloses a kind of preparation method of based lithium-ion battery positive plate, walks including following Suddenly：
Obtain and mend lithium slurry；Wherein, mend lithium slurry and include reproducibility lithium compound, described reproducibility lithium compound includes One of L-AA lithium, D-araboascorbic acid lithium, pyrosulfurous acid lithium, lithium sulfite and phytic acid lithium or multiple.
It is coated on mending lithium slurry at least one surface of the first collector, dry to be formed and mend lithium layer；
Obtain positive-active slurry；
Positive-active slurry is coated on the surface mending lithium layer, dries and form positive-active layer.
The described operation obtaining benefit lithium slurry includes：Reproducibility lithium compound, the second conductive agent and the second binding agent are divided Dissipate and obtain mending lithium slurry in the first solvent, described first solvent includes N-Methyl pyrrolidone, DMF, N, N- dimethyl acetylamide, N, one or more of N- diethylformamide, dimethyl sulfoxide, oxolane, water and alcohol.
Step " being coated on mending lithium slurry at least one surface of the first collector, dry to be formed and mend lithium layer " can be Carry out in the conventional operating condition of lithium ion cell positive and environment, usually, can carry out in air atmosphere.It is dried Condition can select for conventional.Specifically, described drying can be carried out at a temperature of 40～120 DEG C.The holding of described drying The continuous time can be according to drying temperature, and coating speed is selected, typically can be 1～60 minute, preferably 2～30 minutes.
The described operation obtaining positive-active slurry includes：By positive electrode active materials, the first conductive agent and the first binding agent It is scattered in the second solvent and obtains positive-active slurry, described second solvent includes N-Methyl pyrrolidone, N, N- dimethyl methyl Amide, DMAC N,N' dimethyl acetamide, N, one of N- diethylformamide, dimethyl sulfoxide, oxolane, water and alcohol or Multiple.
Step " positive-active slurry being coated on the surface mending lithium layer, dry and form positive-active layer " can be conventional Carry out in the operating condition of lithium ion cell positive and environment, usually, can carry out in air atmosphere.Its condition dried Can select for conventional.Specifically, described drying can be carried out at a temperature of 40～120 DEG C.The persistent period of described drying Can be according to drying temperature, coating speed is selected, typically can be 1～60 minute, preferably 2～30 minutes.
Another embodiment of the present invention also discloses a kind of lithium ion battery, including sealing battery container and be arranged on The electrolyte of described battery container inner space, negative plate, barrier film and positive plate as above, described barrier film be in described just Between pole piece and described negative plate.
Described positive plate and preparation method thereof has been carried out describing in detail above, no longer describes in detail herein.
According to the lithium ion battery of the present invention, described electrolyte, negative plate and barrier film can be those skilled in the art's Conventional selection, is not particularly limited.
Specifically, described electrolyte includes electrolyte lithium salt and nonaqueous solvent.
Described lithium salts is selected from lithium perchlorate, lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, difluoro oxalate boric acid One of lithium, double trifluoromethanesulfonimide lithium, trifluoromethyl sulfonic acid lithium or multiple；Described nonaqueous solvent is selected from ethylene Alkene ester, Allyl carbonate, gamma-butyrolacton, butylene, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, carbonic acid two In propyl ester, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate extremely Few one kind；In described electrolyte, the concentration of lithium salts is 0.5～4.0mol/L, more preferably 0.8～2.0mol/L.
According to the present embodiment, under preferable case, in described electrolyte, also contain film former, it is sub- that described film former is selected from carbonic acid Vinyl acetate, fluorinated ethylene carbonate, in vinylethylene carbonate, ethylene sulfite, propylene sulfite, Isosorbide-5-Nitrae-sulfonic acid fourth At least one in ester, ethyl sulfate；In described electrolyte, film former account for the weight of the gross weight of electrolyte than for 0.1～ 5%.
Described negative plate can adopt negative pole known in the field.In general, described negative plate includes the second afflux Body and be attached to the negative electrode active layer on described second collector.Described second collector can be negative pole commonly used in the art Collector, for example, can be copper mesh, Copper Foil or Punching steel strip.Described negative electrode active layer includes negative active core-shell material, the 3rd bonding Agent and the 3rd conductive agent.
Described negative electrode active material can adopt various negative electrode active materials commonly used in the prior art, for example, graphite, soft Carbon, hard carbon, silicon alloy, tin alloy, silicon crystal, SiOx or a combination thereof or its modifier.
The negative electrode binder that described 3rd binding agent can be commonly used in lithium ion battery, such as polyvinyl alcohol, polytetrafluoro Ethylene, hydroxymethyl cellulose (CMC), Carboxymethyl cellulose sodium, butadiene-styrene rubber (SBR), sodium alginate, sodium polyacrylate, poly- third One of olefin(e) acid ester etc. or two or more.In general, on the basis of the total amount of described negative electrode active layer, described 3rd bonding The content of agent can be 0.5～5 weight %, preferably 1～4 weight %.
The content of described 3rd conductive agent and species are known to those skilled in the art.Specifically, lived with described negative pole On the basis of the total amount of property layer, the content of described 3rd conductive agent can be 0～10 weight %, preferably 1～5 weight %.Described 3rd conductive agent can be one of acetylene black, conductive carbon black, electrically conductive graphite, carbon fiber, CNT and Graphene or two More than kind.Negative pole for example can be lived with the 3rd solvent by the preparation method of described negative pole using various methods commonly used in the art Property material, the 3rd binding agent and optional 3rd conductive agent make negative active material slurry, then by obtained negative pole Active material slurry is coated on the second collector, carry out drying, roll-in, section and soldering polar ear, thus obtaining described negative pole. Described drying can be carried out at a temperature of 60～120 DEG C, and the persistent period of described drying can be 1～60 minute.Described Three solvents can be various solvents used in prior art, such as can be selected from N-Methyl pyrrolidone (NMP), N, N- dimethyl Methanamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), N, N- diethylformamide (DEF), dimethyl sulfoxide (DMSO), four One of hydrogen furan (THF), water and alcohol or two or more.
According to the present invention, described barrier film is arranged between anode pole piece and cathode pole piece, has electrical insulation capability, and ion passes Lead performance and liquid keeps function.Described barrier film can be selected from various barrier films used in lithium ion battery, as micro- in polyolefin many Pore membrane, polyimide porous membrane, barrier film polyethylene felt, glass mat or ultra-fine fibre glass paper and modified composite diaphragm As the ceramic diaphragm of surface-coated ceramics, or surface-coated polymeric membrane such as PVDF (Kynoar), PVDF-HFP is (poly- Biasfluoroethylene-hexafluoropropylene) composite diaphragm etc..The position of described barrier film, property and species by those skilled in the art public affairs Know.
Described lithium ion battery can be prepared using existing method, for example by above-mentioned anode pole piece, barrier film with negative Pole pole piece is overlapped into battery core successively, loads in battery container, injects the electrolyte in battery container, through sealing, chemical conversion, partial volume, Standing is fabricated to lithium ion battery.
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond.
1st, mend the preparation of lithium layer
By L-AA lithium (commercially available), conductive black (purchased from Switzerland Te Migao, the trade mark is super P) and polyvinylidene fluoride Alkene (purchased from Kynar, the trade mark is HSV900) is dispersed in N-Methyl pyrrolidone, is formed and mends lithium slurry.Wherein, L-AA Lithium：Conductive black：The weight of Kynoar is than for 70：20：10, solid content is 40%；
Benefit lithium slurry is coated on the two sides of aluminium foil (thickness is 12 μm), then in 100 DEG C of dryings 5 minutes, thus in aluminum The two sides of paper tinsel is formed mends lithium layer (thickness in monolayer mending lithium layer is 2 μm).
2nd, the preparation of positive-active layer
By cobalt acid lithium LiCoO2, conductive black (purchased from Switzerland Te Migao, the trade mark is super P) and Kynoar (purchase From Kynar, the trade mark is HSV900) it is dispersed in N-Methyl pyrrolidone, form positive-active slurry.Wherein, cobalt acid lithium：Conductive White carbon black：The weight of Kynoar is than for 97：2：1.Solid content is 75%；
Positive-active slurry is coated on the surface mending lithium layer, then in 100 DEG C of dryings 5 minutes, thus mending lithium layer Surface forms positive-active layer.Positive plate (gross thickness is 116 μm) is obtained after roll-in, cutting.
3rd, the preparation of negative pole
Binding agent CMC (sodium carboxymethyl cellulose) is dissolved in water, is subsequently adding negative material native graphite, fully mixed After closing stirring, add SBR SBR emulsion, continue mix and blend.Then this cathode size is uniformly coated to 10 μm The two sides of Copper Foil on, at 100 DEG C toast drying, obtain cathode pole piece precursor after roll-in.Wherein negative material composition weight Than for：Graphite：CMC：SBR=96.5：1.5：2.Wherein, the thickness of negative electrode material layer is 130 μm.
4th, the preparation of lithium ion battery
Respectively above-mentioned positive and negative electrode and polypropylene diaphragm are passed through winding, assembling, be inserted in battery case, after the operation such as baking, By in injection battery aluminum shell appropriate for this conventional electrolyte, sealing, through ageing, chemical conversion, make after the operation such as partial volume lithium from Sub- battery.Mixed solvent in electrolyte therein is than specially EC/EMC/DEC=1：1：1 (volume ratio), its LiPF6's is dense Spend for 1mol/L.
The lithium ion battery being obtained is designated as S1.
Embodiment 2
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond, including most operating procedure in embodiment 1, its difference is：
In the operating procedure of preparation of described benefit lithium layer：Will be (close purchased from Switzerland spy to D-araboascorbic acid lithium, conductive black Height, the trade mark is super P) and Kynoar (purchased from Kynar, the trade mark is HSV900) be dispersed in N-Methyl pyrrolidone, Formed and mend lithium slurry.Wherein, D-araboascorbic acid lithium：Conductive black：The weight of Kynoar is than for 70：20：10, solid content For 40%；
Benefit lithium slurry is coated on the two sides of aluminium foil (thickness is 12 μm), then in 100 DEG C of dryings 5 minutes, thus in aluminum The two sides of paper tinsel is formed mends lithium layer (thickness in monolayer mending lithium layer is 2 μm).
The lithium ion battery being obtained is designated as S2.
Embodiment 3
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond, including most operating procedure in embodiment 1, its difference is：
In the operating procedure of preparation of described benefit lithium layer：In benefit lithium slurry, the ratio of each component is：L-AA lithium：Lead Electric white carbon black：The weight of Kynoar is than for 30：20：50, solid content is 45%.
The lithium ion battery being obtained is designated as S3.
Embodiment 4
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond, including most operating procedure in embodiment 1, its difference is：
In the operating procedure of preparation of described benefit lithium layer：Will be (close purchased from Switzerland spy to lithium sulfite (commercially available), conductive black Height, the trade mark is super P) and Kynoar (purchased from Kynar, the trade mark is HSV900) be dispersed in N-Methyl pyrrolidone, Formed and mend lithium slurry.Wherein, lithium sulfite：Conductive black：The weight of Kynoar is than for 30：20：50, solid content is 45%；
Benefit lithium slurry is coated on the two sides of aluminium foil (thickness is 12 μm), then in 100 DEG C of dryings 5 minutes, thus in aluminum The two sides of paper tinsel is formed mends lithium layer (thickness in monolayer mending lithium layer is 2 μm).
The lithium ion battery being obtained is designated as S4.
Embodiment 5
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond, including most operating procedure in embodiment 4, its difference is：
In the operating procedure of preparation of described benefit lithium layer：In benefit lithium slurry, the ratio of each component is：Lithium sulfite：Conductive charcoal Black：The weight of Kynoar is than for 80：10：10, solid content is 50%.
The lithium ion battery being obtained is designated as S5.
Embodiment 6
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond, including most operating procedure in embodiment 1, its difference is：
By arabo-ascorbic acid lithium (commercially available), CNT and Kynoar (purchased from Kynar, the trade mark is HSV900) dispersion In N-Methyl pyrrolidone, formed and mend lithium slurry.Wherein, arabo-ascorbic acid lithium：CNT：The weight ratio of Kynoar For 65：20：15, solid content is 55%；
Benefit lithium slurry is coated on the two sides of aluminium foil (thickness is 12 μm), then in 100 DEG C of dryings 5 minutes, thus in aluminum The two sides of paper tinsel is formed mends lithium layer (thickness in monolayer mending lithium layer is 2 μm).
The lithium ion battery being obtained is designated as S6.
Embodiment 7
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond, including most operating procedure in embodiment 1, its difference is：
In the operating procedure of preparation of described benefit lithium layer：Will be (special purchased from Switzerland to L-AA lithium (commercially available), conductive black Close height, the trade mark be super P) and Kynoar hexafluoropropene be dispersed in N-Methyl pyrrolidone, formed benefit lithium slurry. Wherein, L-AA lithium：Conductive black：The weight of Kynoar hexafluoropropene is than for 70：20：10, solid content is 40%；
Benefit lithium slurry is coated on the two sides of aluminium foil (thickness is 12 μm), then in 100 DEG C of dryings 5 minutes, thus in aluminum The two sides of paper tinsel is formed mends lithium layer (thickness in monolayer mending lithium layer is 2 μm).
The lithium ion battery being obtained is designated as S7.
Embodiment 8
The present embodiment is used for a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium-ion electric are described Pond, including most operating procedure in embodiment 1, its difference is：
The described bilayer thickness mending lithium layer is 10 μm, and the gross thickness of described positive plate is 122 μm.
The lithium ion battery being obtained is designated as S8.
Comparative example 1
This comparative example be used for comparative illustration a kind of based lithium-ion battery positive plate disclosed by the invention and preparation method thereof, lithium from Sub- battery, comprises the following steps：
1st, the preparation of positive-active layer
By cobalt acid lithium LiCoO2, conductive black (purchased from Switzerland Te Migao, the trade mark is super P) and Kynoar (purchase From Kynar, the trade mark is HSV900) it is dispersed in N-Methyl pyrrolidone, form positive-active slurry.Wherein, cobalt acid lithium：Conductive White carbon black：The weight of Kynoar is than for 97：2：1.Solid content is 75%；
Positive-active slurry is coated on the surface of collector, then in 100 DEG C of dryings 5 minutes, thus in collector Surface forms positive-active layer.Positive plate (gross thickness is 116 μm) is obtained after roll-in, cutting.
3rd, the preparation of negative pole
Binding agent CMC (sodium carboxymethyl cellulose) is dissolved in water, is subsequently adding negative material native graphite, fully mixed After closing stirring, add SBR SBR emulsion, continue mix and blend.Then this cathode size is uniformly coated to 10 μm The two sides of Copper Foil on, at 100 DEG C toast drying, obtain cathode pole piece precursor after roll-in.Wherein negative material composition weight Than for：Graphite：CMC：SBR=96.5：1.5：2.Wherein, the thickness of negative electrode material layer is 130 μm.
4th, the preparation of lithium ion battery
Respectively above-mentioned positive and negative electrode and polypropylene diaphragm are passed through winding, assembling, be inserted in battery case, after the operation such as baking, By in injection battery aluminum shell appropriate for this conventional electrolyte, sealing, through ageing, chemical conversion, make after the operation such as partial volume lithium from Sub- battery.Mixed solvent in electrolyte therein is than specially EC/EMC/DEC=1：1：1 (volume ratio), its LiPF6's is dense Spend for 1mol/L.
The lithium ion battery being obtained is designated as D1.
Performance test
Using following methods, the performance of embodiment 1-8 and the lithium secondary battery of comparative example 1 preparation is evaluated, concrete survey Test result is listed in Table 1.
1. the test of first charge-discharge efficiency.
At normal temperatures, the battery preparing embodiment 1-8 and comparative example 1 respectively is charged 8 little with the electric current of 0.05C When, then 0.2C constant-current charge, to 4.2v, is then charged with constant 4.2v, by electric current 0.02C；Finally with the constant electricity of 0.2C It is 3.0v that stream is discharged to cell voltage.Record charging capacity and discharge capacity.Then first charge-discharge efficiency=(discharge capacity/fill Capacitance) * 100%.
2. cycle performance of battery test.
At normal temperatures, respectively the battery that embodiment 1-8 and comparative example 1 prepare is charged with the electric current of design capacity 1C It is 4.2 volts to voltage, then again with 4.2 volts of chargings of constant voltage, be 0.02C to cut-off current；Put with the constant current of 1C again Electricity to cell voltage is 3.0v.Repeat discharge and recharge 400 times, the discharge capacity after record circulating battery 400 times, and according to following public affairs Formula calculates the capability retention of battery：
Capability retention=(discharge capacity of the discharge capacity/circulate first of the 400th circulation) × 100%
3. inner walkway.
Produce AC internal Resistance tester BS-VR3T to test the internal resistance of cell, battery using Qingtian Industry Co., Ltd., Guangzhou Open-circuit voltage 3.90v.
Table 1
From the results shown in Table 1, the positive pole according to the present invention can effectively improve battery first charge-discharge efficiency, fall Irreversible capacity loss in charge and discharge process for the low lithium secondary battery is such that it is able to the energy improving lithium secondary battery is close Degree.Simultaneously as positive electrode active materials decrease the lithium discharging, the stability of positive electrode active materials obtains and improves, and Mend lithium layer and be arranged on the first collector (i.e. plus plate current-collecting body) and positive-active layer between, will not be to the positive pole in positive pole active layer The normal removal lithium embedded of active substance produces impact, is therefore also obtained using the cycle performance of lithium ion battery of the positive pole of the present invention and carries High.In addition mend the contact impedance that the presence of lithium layer reduces between active material layer and conductive base, reduce the internal resistance of battery, Be conducive to High Current Discharge for Lithium Ion Battery.
It is understood that in various embodiments of the present invention although combine specific collector, electrolyte, every Describe the present invention in detail from film, active substance, binding agent, conductive agent, but, above just for the sake of meeting legal requirement, The present invention does not limit to given embodiment.Those skilled in the art can select according to the announcement of this specification and teaching Suitable collector, electrolyte, isolating membrane, active substance, binding agent and conductive agent.All within the spirit and principles in the present invention Any modification, equivalent and improvement of being made etc., should be included within the scope of the present invention.

Claims (14)

1. a kind of based lithium-ion battery positive plate is it is characterised in that including the first collector, mending lithium layer and positive-active layer；
Described benefit lithium layer is located between described positive-active layer and described first collector；
Described benefit lithium layer includes reproducibility lithium compound, and it is different anti-that described reproducibility lithium compound includes L-AA lithium, D- One of bad hematic acid lithium, pyrosulfurous acid lithium, lithium sulfite and phytic acid lithium or multiple.
2. based lithium-ion battery positive plate according to claim 1 is it is characterised in that described positive-active layer includes positive pole work Property material, the first conductive agent and the first binding agent；
Described positive-active layer includes following components by weight percent：80～99.2 parts of positive electrode active materials, the first conductive agent 0.4～10 Part, 0.4～10 part of the first binding agent.
3. based lithium-ion battery positive plate according to claim 2 is it is characterised in that described positive electrode active materials include lithium cobalt Composite oxides and its modifier, complex Li-Mn-oxide and its modifier, lithium nickel composite oxide and its modifier, iron phosphate Lithium composite xoide and its modifier, lithium manganese phosphate composite oxides and its modifier, phosphoric acid vanadium lithium composite oxides and its change Property thing, many element/transition metals oxidate for lithium and its modifier and lithium-rich manganese-based many element/transition metals oxidate for lithium and its modifier One or more of.
4. based lithium-ion battery positive plate according to claim 2 is it is characterised in that described first conductive agent includes acetylene One or more of black, conductive carbon black, electrically conductive graphite, carbon fiber, CNT and Graphene.
5. based lithium-ion battery positive plate according to claim 2 is it is characterised in that described first binding agent includes fluorine-containing tree One of fat, polyether resin, Cellulose-type binders, rubber adhesive, polyacrylate binding agent and polyimides Or it is multiple.
6. based lithium-ion battery positive plate according to claim 1 is it is characterised in that described benefit lithium layer also includes second leads Electric agent and the second binding agent；
Described benefit lithium layer includes following components by weight percent：10～90 parts of reproducibility lithium compound, the second 5～50 parts of conductive agent, second 5～40 parts of binding agent.
7. based lithium-ion battery positive plate according to claim 6 is it is characterised in that described benefit lithium layer includes following weight group Point：30～80 parts of reproducibility lithium compound, the second 10～30 parts of conductive agent, the second 10～40 parts of binding agent.
8. based lithium-ion battery positive plate according to claim 6 is it is characterised in that described second conductive agent includes acetylene One or more of black, conductive carbon black, electrically conductive graphite, carbon fiber, CNT and Graphene.
9. based lithium-ion battery positive plate according to claim 6 is it is characterised in that described second binding agent includes fluorine-containing tree One of fat, polyether resin, Cellulose-type binders, rubber adhesive, polyacrylate binding agent and polyimides Or it is multiple.
10. based lithium-ion battery positive plate according to claim 1 it is characterised in that the thickness of described benefit lithium layer with described The ratio of the thickness of positive-active layer is 0.02～0.4.
11. based lithium-ion battery positive plates according to claim 10 it is characterised in that the thickness of described benefit lithium layer with described The ratio of the thickness of positive-active layer is 0.04～0.2.
A kind of 12. preparation methoies of based lithium-ion battery positive plate are it is characterised in that comprise the following steps：
Obtain and mend lithium slurry；Wherein, mend lithium slurry and include containing reproducibility lithium compound, described reproducibility lithium compound includes One of L-AA lithium, D-araboascorbic acid lithium, pyrosulfurous acid lithium, lithium sulfite and phytic acid lithium or multiple；
It is coated on mending lithium slurry at least one surface of the first collector, dry to be formed and mend lithium layer；
Obtain positive-active slurry；
Positive-active slurry is coated on the surface mending lithium layer, dries and form positive-active layer.
13. based lithium-ion battery positive plates according to claim 12 are it is characterised in that the operation of lithium slurry is mended in described acquisition Including：Reproducibility lithium compound, the second conductive agent and the second binding agent are scattered in the first solvent and obtain mending lithium slurry, described First solvent includes N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- diethyl formyl One or more of amine, dimethyl sulfoxide, oxolane, water and alcohol.
A kind of 14. lithium ion batteries are it is characterised in that include the positive plate as described in any one in claim 1～11.
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