CN105355819A - Lithium-rich manganese-based high-energy-density lithium-ion battery and preparation method thereof - Google Patents

Lithium-rich manganese-based high-energy-density lithium-ion battery and preparation method thereof Download PDF

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Publication number
CN105355819A
CN105355819A CN201510658469.9A CN201510658469A CN105355819A CN 105355819 A CN105355819 A CN 105355819A CN 201510658469 A CN201510658469 A CN 201510658469A CN 105355819 A CN105355819 A CN 105355819A
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battery
lithium
positive
coated
conductive agent
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周勇
吕敬双
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SHENZHEN HONGTAI BATTERY TECHNOLOGY Co Ltd
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SHENZHEN HONGTAI BATTERY TECHNOLOGY Co 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
    • H01M4/36—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
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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 invention discloses a lithium-rich manganese-based high-energy-density lithium-ion battery and a preparation method thereof. According to the battery, with a lithium-rich manganese-based material doped with lithium vanadium phosphate as a positive electrode and a mixed material of a nano silicon-carbon material and graphite as a negative electrode, through optimal configuration of a conductive agent, a diaphragm, an electrolyte and the like, the influences to the battery performance due to the structure change of the lithium-rich manganese-based material and silicon volume expansion in a cyclic process are effectively reduced. The preparation process of the battery comprises the following steps: active material premixing, pulping, film production, winding/laminating, packaging, liquid injection, secondary packaging, formation, inspection and the like. The battery has the advantages of high energy density, high safety coefficient, relatively long cycle lifetime and the like and can be used as a dynamical chemical power source.

Description

A kind of lithium-rich manganese-based lithium ion battery with high energy density and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of lithium-rich manganese-based lithium ion battery with high energy density and preparation method thereof.
Background technology
From the early 1990s in last century, since lithium ion battery realizes commercialization first, with features such as its high-energy-density, long circulation life, low self-discharge, environmental friendliness, be widely used in portable type electronic product, as mobile phone, notebook computer, electric tool etc.Nearly ten years, along with the progress of material and the raising of production technology, lithium battery is used in just rapidly electric bicycle, hybrid vehicle and pure electric automobile field.Meanwhile, the long course continuation mileage demand of the miniaturization of electronic product, portability development and electric automobile, all an urgent demand lithium ion battery is to the future development of high-energy-density.
Lithium battery is primarily of positive pole, negative pole, barrier film, electrolyte and packaging material composition, and wherein the selection of positive and negative electrode material is the principal element affecting battery energy density size.At present, the lithium ion battery on market all adopts graphite as negative material; The selection kind of positive electrode is relatively many, and digital products is based on cobalt acid lithium and ternary material, and its volume energy density can reach 600Wh/L, and power category product is based on LiFePO4, LiMn2O4, and its mass energy density can reach 150Wh/kg.The energy density proposing to the year two thousand twenty electrokinetic cell during State Council issues " energy-conservation with new-energy automobile estate planning " will reach 300Wh/kg, and obviously the positive and negative electrode material of the existing routine of employing is difficult to meet above requirement.
In recent years, be that the lithium battery of positive pole has been successfully applied on electric automobile with ternary material, its energy density can reach 180Wh/kg.Rich lithium manganese base solid solution material has higher gram volume and platform voltage relative to conventional three-way material, causes the extensive concern of scientific circles and society.Wherein xLi 2mnO 3-(1-x) LiMn 1/3ni 1/3co 1/3o 2research relative maturity, but still it is poor to there is conductance, and in cyclic process, structural change causes the problem such as operating voltage and reversible capacity reduction.
Silicon materials have the theoretical gram volume of 4200mAh/g and the actual gram volume higher than 1000mAh/g, and belong to same main group with carbon, are regarded as the first-selection of lithium cell cathode material of future generation.But volumetric expansion causes capacitance loss seriously to constrain development and the application of silicon materials after circulation.
Summary of the invention
The object of the invention is the defect for above-mentioned positive and negative electrode material, by implementing practicable prioritization scheme, providing a kind of high-energy-density, macrocyclic lithium ion battery.
The present invention adopts following technical scheme:
Lithium-rich manganese-based lithium ion battery with high energy density of the present invention, is made up of positive pole, negative pole, barrier film, electrolyte and packaging material, and this anode is coated on aluminum metal collector by the slurry of positive pole being, conductive agent, binding agent and solvent composition; This battery cathode is coated in copper metal collector by the slurry of negative pole being, conductive agent, thickener, binding agent and solvent composition.
Described positive pole being is made up of the main being of positive pole and the second being, and the main being of positive pole is the coated rich lithium manganese base solid solution xLi of metal oxide 2mnO 3-(1-x) LiMn 1/3ni 1/3co 1/3o 2, 0<x<0.5, metal oxide is Al 2o 3, ZnO, ZrO 2, TiO 2in one, Li 3v 2(PO 4) 3it is the second being.
Positive conductive agent is one or more in superconductive carbon black, flaky graphite, carbon nano-tube, carbon fiber etc., and the binding agent of positive pole is Kynoar (PVDF); Positive pole solvent is 1-METHYLPYRROLIDONE (NMP).
Described negative pole being is made up of the main being of negative pole and the second being, and the main being of negative pole is the coated nanometer silicon carbide of carbon, and the second being is Delanium or native graphite.
Cathode conductive agent is one or more in superconductive carbon black and Graphene, flaky graphite etc., and the thickener of this negative pole is sodium carboxymethylcellulose (CMC), and binding agent is butadiene-styrene rubber (SBR) emulsion; Negative pole solvent is deionized water.
In anode sizing agent, the proportion of composing of solid phase material is: the mass ratio of being, PVDF, conductive agent is (92-97): (1-4): (1-4), wherein the second being Li in positive pole being 3v 2(PO 4) 3account for the 1%-10% of positive pole being total weight, in conductive agent, CNT accounts for more than 25% of conductive agent gross mass; In cathode size, the proportion of composing of solid phase material is: the mass ratio of negative pole being, CMC, conductive agent, SBR is (92-96): (1-2): (1-3): (2-3), wherein in negative pole being, the second being graphite accounts for the 10%-40% of negative pole being gross mass, and in conductive agent, Graphene accounts for the 25%-75% of conductive agent gross mass.
The barrier film of this battery is the ceramic diaphragm that single or double scribbles aluminium oxide, and the barrier film composition before coating is individual layer PP material or multilayer PE/PP composite.
Described electrolyte is made up of electrolyte, electrolyte solvent and additive, electrolyte solvent be high voltage withstanding solvent in organic carbonate class, organic carboxylic ester class, fluorinated esters class, ethers, sulfone class etc. more than one; Electrolyte is LiPF 6, LiBF 4, LiClO 4, LiAsO 6, Li (CF 3sO 2) 2n, LiCF 3sO 3in one or more high pressure resistant electrolyte; Additive is for containing fluoro base class organic substance.
The one that the packaging material of this battery are aluminum plastic film, aluminum hull, box hat or mould in shell, specifically determines according to product requirement.
The concrete steps of the preparation method of lithium ion battery of the present invention are as follows:
Step 1, the preparation of anode sizing agent:
By xLi coated for metal oxide 2mnO 3-(1-x) LiMn 1/3ni 1/3co 1/3o 2with Li 3v 2(PO 4) 3mixing and ball milling 4-24h, is dissolved in PVDF in NMP, adds conductive agent, mixing being successively, after high speed dispersion, viscosity is adjusted to 6000-12000cp, obtains anode sizing agent to be coated;
Step 2, the preparation of cathode size:
By carbofrax material (carborundum quality 60%-90%) coated for carbon and Delanium mixing and ball milling 4-24h, CMC is dissolved and is made into the glue that mass fraction is 1.7% in deionized water, add conductive agent, negative pole being successively, be adjusted to after high speed dispersion and viscosity is adjusted to 2500-3500cp, add SBR emulsion, after low rate mixing, obtain cathode size to be coated;
Step 3, the making of positive and negative electrode pole piece:
Positive and negative electrode slurry is carried out be coated with, roll-in, itemize, die-cut after obtain meeting the positive and negative electrode pole piece of dimensional requirement;
Step 4, the making of naked battery core:
The pole piece that step 3 is made and barrier film, adopt the mode of winding or lamination by " barrier film-positive pole-barrier film-negative pole " order multilayer folding successively, after fixing with adhesive tape, positive and negative electrode is welding of aluminum lug, nickel lug or copper nickel plating lug respectively;
Step 5, enters shell and top, side seal:
Naked battery core in step 4 is loaded housing, is placed in baking oven, removing moisture;
Step 6, fluid injection, an envelope:
Under the environment of dew point lower than-30 DEG C, take out battery core in step 5, inject appropriate high voltage withstanding electrolyte, encapsulation, aging;
Step 7, changes into, two envelopes:
Aging rear battery is carried out precharge change into, after changing into, need degasification be carried out, secondary encapsulation;
Step 8, cell inspection;
Battery will be changed into carry out partial volume, the test of K value, after visual examination, the high-energy-density battery core meeting application claims can be obtained.
The xLi that the main being of positive pole adopts metal oxide coated 2mnO 3-(1-x) LiMn 1/3ni 1/3co 1/3o 2.X value gets 0<x<0.5, and value is on the low side is beneficial to the stable of material structure; Metal oxide adopts Al 2o 3, ZnO, ZrO 2, TiO 2deng, in cyclic process, protective material structure is stable.
Positive electrode adds the Li of 1%-10% 3v 2(PO 4) 3improve high temperature performance and the cyclical stability of battery.
Positive pole adds conductivity ability and the liquid storage performance of the CNT raising material of 1%-3%, optimizes multiplying power and the cycle performance of battery.
The main being of negative pole adopts through the coated nano silicon carbide silicon composite of vapour deposition process carbon.Nanometer silicon carbide, because particle diameter is little, conjugation is high, effectively can be alleviated silicon and to expand the capacitance loss caused; Vapour deposition process can realize the integral coating to silicon carbon material, effectively can suppress the volumetric expansion of silicon in cyclic process.
Add 1%-40% artificial/native graphite, realize, to the coated rear slurrying of its secondary, effectively to improve the cycle life of battery with above-mentioned silicon carbon material high speed spheroidal graphite.
Negative pole adds the Graphene of 1%-3%, optimizes electric conductivity and the compaction capacity of negative pole.
Electrolyte adopt high voltage withstanding solvent in organic carbonate class, organic carboxylic ester class, fluorinated esters class, ethers, sulfone class etc. more than one as solvent, add containing fluoro base class organic substance as additive, improve the high voltage performance of electrolyte further; Adopt LiPF 6, LiBF 4, LiClO 4, LiAsO 6, Li (CF 3sO 2) 2n, LiCF 3sO 3in one or more as electrolyte.
Battery diaphragm adopts single or double to be coated with PP film or the PP/PE composite membrane of pottery, improves security performance and the high voltage performance of battery.
Technical advantage of the present invention is embodied in:
The lithium-rich manganese base material that the main being of positive pole adopts the metal oxide of high-energy-density coated, mix good cycle, lithium vanadium phosphate material that coefficient of safety is high, effectively can suppress the structural change in lithium-rich manganese base material cyclic process, make composite material have high-energy-density and macrocyclic excellent specific property concurrently like this; The nano-silicone wire/carbon material that negative pole adopts the carbon of high power capacity coated, as main being, after Conventional graphite material high speed ball milling, achieves the secondary of silicon carbon material coated, effectively can reduce silicon in cyclic process and to expand the capacitance loss caused; In addition, positive and negative electrode adds CNT and Graphene respectively and adopts ceramic diaphragm, the electrolyte applied to adopt fluoro base class organic substance as design features such as the high pressure resistant electrolyte of additive as additive, barrier film, and the battery made for this patent has the features such as high-energy-density, long circulation life, high safety performance and provides strong support.
Accompanying drawing explanation
Fig. 1 is the fabrication processing figure of anode sizing agent in embodiments of the invention 1;
Wherein, a1-Al 2o 3coated 0.3Li 2mnO 3-0.7LiMn 1/3ni 1/3co 1/3o 2with Li 3v 2(PO 4) 3mixing and ball milling, a2-PVDF are dissolved in NMP, a3-and add CNT slurry and S-P, a4-and add the mixing being, the a5-that prepare in operation a1 and add NMP.
Fig. 2 is the fabrication processing figure of negative pole in embodiments of the invention 1;
Wherein, the silicon carbon material that CMC is dissolved in deionized water with Delanium mixing and ball milling, b2-by the carbofrax material that b1-carbon is coated, b3-adds watersoluble plumbago alkene slurries and technique b1 is prepared by S-P, b4-and graphite mix being join add in the glue of conductive agent, b5-adds water adjusting viscosity, b6-adds SBR emulsion.Fig. 3 is the fabrication processing of lithium-rich manganese-based lithium ion battery in embodiments of the invention 1;
Wherein, c1-positive and negative electrode pole piece making, the making of the naked battery core of c2-battery, the naked battery core of c3-enters shell and top side seal operation, c4-fluid injection and an envelope operation, c5-change into, two envelope operations, c6-capacity, internal resistance, K value are measured and size appearance inspection.
Embodiment
In order to make design of the present invention, implementation process, technical characterstic clear and definite more, below in conjunction with drawings and Examples to inventing the elaboration carried out specifically.
In the present invention, if not special instruction, all percentage is mass percent, and raw materials used and equipment is the general raw material in this field and conventional equipment.
Embodiment 1
The preparation of positive and negative electrode slurry is one of key of obtaining of this patent battery excellent properties, at this, 1 is described in detail with accompanying drawing 2 by reference to the accompanying drawings.
The preparation of anode sizing agent, is shown in accompanying drawing 1.Operation a1,95:5 is by Al in mass ratio 2o 3coated 0.3Li 2mnO 3-0.7LiMn 1/3ni 1/3co 1/3o 2with Li 3v 2(PO 4) 3mixing and ball milling 4-24h; Operation a2, is dissolved in PVDF in NMP and is made into the glue that mass fraction is 10%; Operation a3, adds CNT slurry, after high speed dispersion 1h, adds S-P high-speed stirred 1-2h; Operation a4, divides and adds the mixing being prepared in operation a1 for 3-5 time, stirs 3-6h; Operation a5, adds a small amount of NMP, viscosity is adjusted to 6000-12000cp, obtains anode sizing agent to be coated.The proportioning of this anode sizing agent being, CNT, S-P, PVDF is 94:1:2:3.
The preparation of cathode size, is shown in accompanying drawing 2.Operation b1, by carbofrax material (carborundum quality accounts for 80%) coated for carbon and Delanium 80:20 mixing and ball milling 4-24h in mass ratio; Operation b2, is dissolved in CMC in deionized water and is made into the glue that mass fraction is 1.7%; Operation b3, adds watersoluble plumbago alkene slurries, after high speed dispersion 1h, adds S-P high-speed stirred 1-2h; Operation b4, the being that mixes of the silicon carbon material prepared by technique b1 and graphite divides to join for 3-5 time and has added in the glue of conductive agent, stirs 3-6h; Operation b5, adds appropriate water and viscosity is adjusted to 2000-3500cp; Operation b6, adds SBR emulsion, stirs 0.5-2h slowly and obtains cathode size to be coated.The proportioning of this cathode size being, Graphene, S-P, CMC, SBR is 94.5:0.5:1:1.5:2.5, and wherein SBR refers to solid masses in SBR emulsion.
The making of positive and negative electrode pole piece, accompanying drawing 3-c1.Positive and negative electrode slurry is carried out be coated with, roll-in, itemize, die-cut after obtain meeting the positive and negative electrode pole piece of dimensional requirement.
The making of the naked battery core of battery, accompanying drawing 3-c2.Adopt lamination process by " barrier film-positive pole-barrier film-negative pole " order multilayer folding successively, after fixing with adhesive tape, positive and negative electrode is welding of aluminum lug, nickel lug respectively.
Naked battery core enters shell and top side seal operation, accompanying drawing 3-c3.Naked battery core is placed in the aluminum plastic film rushing hole, regulates suitable temperature, pressure, time, battery is carried out closedtop and side seal.
Fluid injection and an envelope operation, accompanying drawing 3-c4.The battery completed by top side seal, after baking dewaters, injects containing the organic high voltage withstanding electrolyte of fluoro base class, is honored as a queen, proceeds to high-temperature aging room to be changed through one.
Change into, two envelope operations, accompanying drawing 3-c5.Aging rear battery is carried out precharge change into, this operation divides two steps to carry out, and carries out low current charge before 3.4V, carries out larger current and charge to 4.2V after 3.4V.After 4-24h shelved by rechargeable battery, carry out except sealing gland operation, i.e. two envelopes.
Capacity, internal resistance, K value are measured and size appearance inspection, accompanying drawing 3-c6.Battery will be changed into measure through partial volume, inner walkway, K value and after size appearance passed examination, namely obtain resultant battery.
Embodiment 2
The preparation of anode sizing agent, is shown in accompanying drawing 1.Operation a1,98:2 is by Al in mass ratio 2o 3coated 0.3Li 2mnO 3-0.7LiMn 1/3ni 1/3co 1/3o 2with Li 3v 2(PO 4) 3mixing and ball milling 4-24h; Operation a2, is dissolved in PVDF in NMP and is made into the glue that mass fraction is 10%; Operation a3, adds CNT slurry, after high speed dispersion 1h, adds S-P high-speed stirred 1-2h; Operation a4, divides and adds the mixing being prepared in operation a1 for 3-5 time, stirs 3-6h; Operation a5, adds a small amount of NMP, viscosity is adjusted to 6000-12000cp, obtains anode sizing agent to be coated.The proportioning of this anode sizing agent being, CNT, S-P, PVDF is 94:1:2:3.
The preparation of cathode size, is shown in accompanying drawing 2.Operation b1, by carbofrax material (carborundum quality accounts for 80%) coated for carbon and Delanium 85:15 mixing and ball milling 4-24h in mass ratio; Operation b2, is dissolved in CMC in deionized water and is made into the glue that mass fraction is 1.7%; Operation b3, adds watersoluble plumbago alkene slurries, after high speed dispersion 1h, adds S-P high-speed stirred 1-2h; Operation b4, the being that mixes of the silicon carbon material prepared by technique b1 and graphite divides to join for 3-5 time and has added in the glue of conductive agent, stirs 3-6h; Operation b5, adds appropriate water and viscosity is adjusted to 2000-3500cp; Operation b6, adds SBR emulsion, stirs 0.5-2h slowly and obtains cathode size to be coated.The proportioning of this cathode size being, Graphene, S-P, CMC, SBR is 94.5:0.5:1:1.5:2.5, and wherein SBR refers to solid masses in SBR emulsion.
The making of positive and negative electrode pole piece, accompanying drawing 3-c1.Positive and negative electrode slurry is carried out be coated with, roll-in, itemize, die-cut after obtain meeting the positive and negative electrode pole piece of dimensional requirement.
The making of the naked battery core of battery, accompanying drawing 3-c2.Adopt lamination process by " barrier film-positive pole-barrier film-negative pole " order multilayer folding successively, after fixing with adhesive tape, positive and negative electrode is welding of aluminum lug, nickel lug respectively.
Naked battery core enters shell and top side seal operation, accompanying drawing 3-c3.Naked battery core is placed in the aluminum plastic film rushing hole, regulates suitable temperature, pressure, time, battery is carried out closedtop and side seal.
Fluid injection and an envelope operation, accompanying drawing 3-c4.The battery completed by top side seal, after baking dewaters, injects containing the organic high voltage withstanding electrolyte of fluoro base class, is honored as a queen, proceeds to high-temperature aging room to be changed through one.
Change into, two envelope operations, accompanying drawing 3-c5.Aging rear battery is carried out precharge change into, this operation divides two steps to carry out, and carries out low current charge before 3.4V, carries out larger current and charge to 4.2V after 3.4V.After 4-24h shelved by rechargeable battery, carry out except sealing gland operation, i.e. two envelopes.
Capacity, internal resistance, K value are measured and size appearance inspection, accompanying drawing 3-c6.Battery will be changed into measure through partial volume, inner walkway, K value and after size appearance passed examination, namely obtain resultant battery.
Embodiment 3
The preparation of anode sizing agent, is shown in accompanying drawing 1.Operation a1,95:5 is by Al in mass ratio 2o 3coated
0.5Li 2mnO 3-0.5LiMn 1/3ni 1/3co 1/3o 2with Li 3v 2(PO 4) 3mixing and ball milling 4-24h; Operation a2, is dissolved in PVDF in NMP and is made into the glue that mass fraction is 10%; Operation a3, adds CNT slurry, after high speed dispersion 1h, adds S-P high-speed stirred 1-2h; Operation a4, divides and adds the mixing being prepared in operation a1 for 3-5 time, stirs 3-6h; Operation a5, adds a small amount of NMP, viscosity is adjusted to 6000-12000cp, obtains anode sizing agent to be coated.The proportioning of this anode sizing agent being, CNT, S-P, PVDF is 94:1:2:3.
The preparation of cathode size, is shown in accompanying drawing 2.Operation b1, by carbofrax material (carborundum quality accounts for 80%) coated for carbon and Delanium 90:10 mixing and ball milling 4-24h in mass ratio; Operation b2, is dissolved in CMC in deionized water and is made into the glue that mass fraction is 1.7%; Operation b3, adds watersoluble plumbago alkene slurries, after high speed dispersion 1h, adds S-P high-speed stirred 1-2h; Operation b4, the being that mixes of the silicon carbon material prepared by technique b1 and graphite divides to join for 3-5 time and has added in the glue of conductive agent, stirs 3-6h; Operation b5, adds appropriate water and viscosity is adjusted to 2000-3500cp; Operation b6, adds SBR emulsion, stirs 0.5-2h slowly and obtains cathode size to be coated.The proportioning of this cathode size being, Graphene, S-P, CMC, SBR is 94.5:0.5:1:1.5:2.5, and wherein SBR refers to solid masses in SBR emulsion.
The making of positive and negative electrode pole piece, accompanying drawing 3-c1.Positive and negative electrode slurry is carried out be coated with, roll-in, itemize, die-cut after obtain meeting the positive and negative electrode pole piece of dimensional requirement.
The making of the naked battery core of battery, accompanying drawing 3-c2.Adopt lamination process by " barrier film-positive pole-barrier film-negative pole " order multilayer folding successively, after fixing with adhesive tape, positive and negative electrode is welding of aluminum lug, nickel lug respectively.
Naked battery core enters shell and top side seal operation, accompanying drawing 3-c3.Naked battery core is placed in the aluminum plastic film rushing hole, regulates suitable temperature, pressure, time, battery is carried out closedtop and side seal.
Fluid injection and an envelope operation, accompanying drawing 3-c4.The battery completed by top side seal, after baking dewaters, injects containing the organic high voltage withstanding electrolyte of fluoro base class, is honored as a queen, proceeds to high-temperature aging room to be changed through one.
Change into, two envelope operations, accompanying drawing 3-c5.Aging rear battery is carried out precharge change into, this operation divides two steps to carry out, and carries out low current charge before 3.4V, carries out larger current and charge to 4.2V after 3.4V.After 4-24h shelved by rechargeable battery, carry out except sealing gland operation, i.e. two envelopes.
Capacity, internal resistance, K value are measured and size appearance inspection, accompanying drawing 3-c6.Battery will be changed into measure through partial volume, inner walkway, K value and after size appearance passed examination, namely obtain resultant battery.
Comparative example 1
The preparation of anode sizing agent.PVDF is dissolved in NMP and is made into the glue that mass fraction is 10%; Add S-P high-speed stirred 1-2h; Divide and add positive pole being LiMn for 3-5 time 1/3ni 1/3co 1/3o 2, stir 3-6h; Add a small amount of NMP, viscosity is adjusted to 6000-12000cp, obtain anode sizing agent to be coated.The proportioning of this anode sizing agent being, S-P, PVDF is 94:3:3.
The preparation of cathode size.CMC is dissolved in deionized water and is made into the glue that mass fraction is 1.7%; Add S-P high-speed stirred 1-2h; Artificial graphite material is divided join for 3-5 time and added in the glue of conductive agent, stir 3-6h; Add appropriate water and viscosity is adjusted to 2000-3500cp; Add SBR emulsion, stir 0.5-2h slowly and obtain cathode size to be coated.The proportioning of this cathode size being, S-P, CMC, SBR is 94.5:1.5:1.5:2.5, and wherein SBR refers to solid masses in SBR emulsion.
The making of positive and negative electrode pole piece.Positive and negative electrode slurry is carried out be coated with, roll-in, itemize, die-cut after obtain meeting the positive and negative electrode pole piece of dimensional requirement.
The making of the naked battery core of battery.Adopt lamination process by " barrier film-positive pole-barrier film-negative pole " order multilayer folding successively, after fixing with adhesive tape, positive and negative electrode is welding of aluminum lug, nickel lug respectively.
Naked battery core enters shell and top side seal operation.Naked battery core is placed in the aluminum plastic film rushing hole, regulates suitable temperature, pressure, time, battery is carried out closedtop and side seal.
Fluid injection and an envelope operation.The battery completed by top side seal, after baking dewaters, injects normal conventional potential electrolysis liquid, is honored as a queen, proceeds to high-temperature aging room to be changed through one.
Change into, two envelope operations.Aging rear battery is carried out precharge change into, this operation divides two steps to carry out, and carries out low current charge before 2.8V, carries out larger current and charge to 3.9V after 2.8V.After 4-24h shelved by rechargeable battery, carry out except sealing gland operation, i.e. two envelopes.
Capacity, internal resistance, K value are measured and size appearance inspection.Battery will be changed into measure through partial volume, inner walkway, K value and after size appearance passed examination, namely obtain resultant battery.
This comparative example battery makes by the technological process of production of the ternary material battery of existing market industrialization.
The qualified battery core of Example and each 1000pcs of comparative example at room temperature carries out charge-discharge performance test, and embodiment battery core test voltage scope is 2.75-4.8V, and comparative example battery core test voltage scope is 2.75-4.2V, and its test result statistics is as follows:
As can be seen from test result, its volume energy density of battery that this patent is produced can reach 800Wh/L, and mass energy density can reach 300Wh/kg, far above conventional three-way material battery core; Battery 0.5C 300 capability retentions that circulate that this patent is produced exceed or close to 80%, can meet the instructions for use of digital battery core; But lower than conventional three-way material battery core in long circulating test, if use as power battery core, its cycle performance still haves much room for improvement.
By the targeted design to optimization of material proportioning and cell making process, it is high that the battery that the present invention makes has energy density, and the good feature of cycle performance is the ideal chose of high-energy-density digital battery and electrokinetic cell.
Below be only preferred embodiment provided by the invention, the present invention can not be limited with this.Every any within design principle of the present invention and spirit substitutes, amendment, optimization etc., all should be included within protection scope of the present invention.

Claims (10)

1. a lithium-rich manganese-based lithium ion battery with high energy density, be made up of positive pole, negative pole, barrier film, electrolyte and packaging material, it is characterized in that: this anode is coated on aluminum metal collector by the slurry of positive pole being, conductive agent, binding agent and solvent composition; This battery cathode is coated in copper metal collector by the slurry of negative pole being, conductive agent, thickener, binding agent and solvent composition.
2. lithium ion battery as claimed in claim 1, is characterized in that: described positive pole being is made up of the main being of positive pole and the second being, and the main being of positive pole is the coated rich lithium manganese base solid solution xLi of metal oxide 2mnO 3-(1-x) 1liMn / 3ni 1/3co 1/3o 2, 0<x<0.5, metal oxide is Al 2o 3, ZnO, ZrO 2, TiO 2in one, wherein metal oxide quality accounts for the 1%-3% of this being gross mass; Li 3v 2(PO 4) 3it is the second being.
3. lithium ion battery as claimed in claim 2, is characterized in that: positive conductive agent is one or more in superconductive carbon black, flaky graphite, carbon nano-tube, carbon fiber etc., and the binding agent of positive pole is Kynoar (PVDF); Positive pole solvent is 1-METHYLPYRROLIDONE (NMP).
4. lithium ion battery as claimed in claim 3, it is characterized in that: described negative pole being is made up of the main being of negative pole and the second being, the main being of negative pole is the coated nanometer silicon carbide of carbon, and wherein carborundum quality accounts for 50%-90%, and the second being is Delanium or native graphite.
5. lithium ion battery as claimed in claim 4, it is characterized in that: cathode conductive agent is one or more in superconductive carbon black and Graphene, flaky graphite etc., the thickener of this negative pole is sodium carboxymethylcellulose (CMC), and binding agent is butadiene-styrene rubber (SBR) emulsion; Negative pole solvent is deionized water.
6. lithium ion battery as claimed in claim 5, it is characterized in that: in anode sizing agent, the proportion of composing of solid phase material is: the mass ratio of being, PVDF, conductive agent is (92-97): (1-4): (1-4), wherein the second being Li in positive pole being 3v 2(PO 4) 3account for the 1%-10% of positive pole being total weight, in conductive agent, CNT accounts for more than 25% of conductive agent gross mass; In cathode size, the proportion of composing of solid phase material is: the mass ratio of negative pole being, CMC, conductive agent, SBR is (92-96): (1-2): (1-3): (2-3), wherein in negative pole being, the second being graphite accounts for the 10%-40% of negative pole being gross mass, and in conductive agent, Graphene accounts for the 25%-75% of conductive agent gross mass.
7. lithium ion battery as claimed in claim 1, it is characterized in that: the barrier film of this battery is the ceramic diaphragm that single or double scribbles aluminium oxide, the barrier film composition before coating is individual layer PP material or multilayer PE/PP composite.
8. lithium ion battery as claimed in claim 1, it is characterized in that: described electrolyte is made up of electrolyte, electrolyte solvent and additive, electrolyte solvent be high voltage withstanding solvent in organic carbonate class, organic carboxylic ester class, fluorinated esters class, ethers, sulfone class more than one; Electrolyte is LiPF 6, LiBF 4, LiClO 4, LiAsO 6, Li (CF 3sO 2) 2n, LiCF 3sO 3in one or more high pressure resistant electrolyte; Additive is for containing fluoro base class organic substance.
9. lithium ion battery as claimed in claim 1, is characterized in that: the one that the packaging material of this battery are aluminum plastic film, aluminum hull, box hat or mould in shell, specifically determines according to product requirement.
10. prepare a method for lithium ion battery as claimed in claim 6, it is characterized in that: the concrete steps of described method are as follows:
Step 1, the preparation of anode sizing agent:
By xLi coated for metal oxide 2mnO 3-(1-x) LiMn 1/3ni 1/3co 1/3o 2with Li 3v 2(PO 4) 3mixing and ball milling 4-24h, is dissolved in PVDF in NMP, adds conductive agent, mixing being successively, after high speed dispersion, viscosity is adjusted to 6000-12000cp, obtains anode sizing agent to be coated;
Step 2, the preparation of cathode size:
By carbofrax material (carborundum quality 60%-90%) coated for carbon and Delanium mixing and ball milling 4-24h, CMC is dissolved and is made into the glue that mass fraction is 1.7% in deionized water, add conductive agent, negative pole being successively, be adjusted to after high speed dispersion and viscosity is adjusted to 2500-3500cp, add SBR emulsion, after low rate mixing, obtain cathode size to be coated;
Step 3, the making of positive and negative electrode pole piece:
Positive and negative electrode slurry is carried out be coated with, roll-in, itemize, die-cut after obtain meeting the positive and negative electrode pole piece of dimensional requirement;
Step 4, the making of naked battery core:
The pole piece that step 3 is made and barrier film, adopt the mode of winding or lamination by " barrier film-positive pole-barrier film-negative pole " order multilayer folding successively, after fixing with adhesive tape, positive and negative electrode is welding of aluminum lug, nickel lug or copper nickel plating lug respectively;
Step 5, enters shell and top, side seal:
Naked battery core in step 4 is loaded housing, is placed in baking oven, removing moisture;
Step 6, fluid injection, an envelope:
Under the environment of dew point lower than-30 DEG C, take out battery core in step 5, inject appropriate high voltage withstanding electrolyte, encapsulation, aging;
Step 7, changes into, two envelopes:
Aging rear battery is carried out precharge change into, after changing into, need degasification be carried out, secondary encapsulation;
Step 8, cell inspection;
Battery will be changed into carry out partial volume, the test of K value, after visual examination, the high-energy-density battery core meeting application claims can be obtained.
CN201510658469.9A 2015-10-13 2015-10-13 Lithium-rich manganese-based high-energy-density lithium-ion battery and preparation method thereof Pending CN105355819A (en)

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CN106784726A (en) * 2017-01-18 2017-05-31 长安大学 Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof
CN107204428A (en) * 2017-06-16 2017-09-26 中南大学 A kind of method of phosphoric acid vanadium lithium coated lithium ion battery ternary material
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CN111082009A (en) * 2019-12-17 2020-04-28 中南大学 Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof
CN111207980A (en) * 2020-03-01 2020-05-29 东北石油大学 Method for manufacturing three-layer heterogeneous flat plate core pressure monitoring point
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CN105932325A (en) * 2016-07-18 2016-09-07 上海空间电源研究所 Long-storage life lithium ion storage battery
CN107644997A (en) * 2016-07-20 2018-01-30 三星环新（西安）动力电池有限公司 A kind of positive electrode surface coating modification method based on sodium carboxymethylcellulose
CN106784726B (en) * 2017-01-18 2020-02-07 长安大学 Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof
CN106784726A (en) * 2017-01-18 2017-05-31 长安大学 Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof
CN107204428A (en) * 2017-06-16 2017-09-26 中南大学 A kind of method of phosphoric acid vanadium lithium coated lithium ion battery ternary material
CN107293727A (en) * 2017-07-24 2017-10-24 广州市云通磁电股份有限公司 A kind of positive electrode, lithium ion battery comprising the positive electrode and preparation method thereof
CN107887594A (en) * 2017-12-04 2018-04-06 中国科学院青岛生物能源与过程研究所 A kind of compound lithium-rich manganese-based anode material and preparation method for lithium ion battery
CN109817868A (en) * 2018-12-25 2019-05-28 中国电子科技集团公司第十八研究所 High-voltage and high-safety lithium ion battery and preparation method thereof
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CN111082009A (en) * 2019-12-17 2020-04-28 中南大学 Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof
CN111082009B (en) * 2019-12-17 2021-04-09 中南大学 Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof
CN111207980A (en) * 2020-03-01 2020-05-29 东北石油大学 Method for manufacturing three-layer heterogeneous flat plate core pressure monitoring point
CN111446504A (en) * 2020-04-02 2020-07-24 新乡华锐锂电新能源有限公司 Rapid formation and grading method for soft package battery using high-voltage electrolyte

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