CN107785537A - A kind of method of modifying of new type lithium ion battery anode pole piece, its purposes and pole piece - Google Patents

A kind of method of modifying of new type lithium ion battery anode pole piece, its purposes and pole piece Download PDF

Info

Publication number
CN107785537A
CN107785537A CN201710771251.3A CN201710771251A CN107785537A CN 107785537 A CN107785537 A CN 107785537A CN 201710771251 A CN201710771251 A CN 201710771251A CN 107785537 A CN107785537 A CN 107785537A
Authority
CN
China
Prior art keywords
pole piece
ion battery
lithium ion
lithium
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710771251.3A
Other languages
Chinese (zh)
Other versions
CN107785537B (en
Inventor
朱蕾
汤卫平
贾荻
江小标
吴勇民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Space Power Sources
Original Assignee
Shanghai Institute of Space Power Sources
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Space Power Sources filed Critical Shanghai Institute of Space Power Sources
Priority to CN201710771251.3A priority Critical patent/CN107785537B/en
Publication of CN107785537A publication Critical patent/CN107785537A/en
Application granted granted Critical
Publication of CN107785537B publication Critical patent/CN107785537B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses the method for modifying of a kind of new type lithium ion battery anode pole piece, its purposes and pole piece, this method includes：Step 1, modification pole piece is prepared：Slurry containing the first material is formed into first coating coated in aluminium foil side, drying, obtains modifying pole piece；Step 2, second coating will be formed in first coating of the slurry containing positive electrode active materials coated in above-mentioned modification pole piece, dried, obtain lithium ion battery modification anode pole piece；Wherein, the working voltage platform of first material is less than positive electrode active materials.The method of modifying is easy to operate, has universality, is easy to industrialize.The lithium ion battery assembled using the modification anode pole piece of the present invention can shorten the transmission path of lithium ion/electronics in charge and discharge process, reduce interface impedance, bring higher efficiency for charge-discharge, specific discharge capacity and excellent high rate performance.

Description

A kind of method of modifying of new type lithium ion battery anode pole piece, its purposes and pole piece
Technical field
The invention belongs to electrochemical field, is related to a kind of anode preparation method, more particularly to a kind of to lithium-ion electric The method that pond anode pole piece is modified.
Background technology
With the development of economy and society, energy shortage turns into the Tough questions that world community faces, and this promotes the mankind Constantly seek the novel environment friendly energy.Compared with traditional cadmium nickel, Ni-H cell, lithium ion battery has, work electricity higher than energy Pressure is high, temperature limit is wide, self-discharge rate is low, the advantages that having extended cycle life, and is widely used in mobile phone, notebook electricity Brain and other portable electronics, and progressively to high-power system such as electric automobile, intelligent grid, satellite and distributed energy system The fields such as system are expanded.
From the point of view of current development situation, countries in the world also all propose middle length to high-energy-density chemical energy storage power supply Phase development plan, such as NASA（National Aeronautics and Space Administration, American National boat Empty and space travel office）It is true all by the ratio energy object of recent lithium ion battery with battery manufacturers Saft companies of Air France Group etc. It is set to 250 ~ 300 Wh/kg, Japanese NEDO（The New Energy and Industrial Technology Development Organization, New Energy and Industrial Technology Development Organization）Power battery of electric vehicle develops The energy density of the year two thousand twenty energy type lithium ion battery is also illustrated that in planning will reach 250Wh/kg.
However, the energy density of lithium ion battery is primarily limited to positive electrode, because commercial carbon material used as anode specific volume Measure in 300 ~ 350 mAh/g or so, and common positive electrode（Including LiCoO2、LiNiO2, spinel-type LiMn2O4, stratiform LiMnO2、LiFePO4、Li[Ni1/3Co1/3Mn1/3]O2Deng）Specific capacity be 120 ~ 165 mAh/g, far below the reason of negative material By capacity.
With the continuous social and economic development with the rapid emergence of other industries, market still needs with higher performance Accumulation power supply appears on the market, and the selection of electrode material is to determine the key point of its performance in accumulation power supply.Positive pole in electrode material Material and the uneven serious rapid development for limiting high-energy-density accumulation power supply of extreme of negative material capacity development, therefore from The preparation of material, the optimization of material, battery design, preparation technology angularly start with, and develop with higher capacity, more dominance energy Anode material for lithium-ion batteries it is most important.
The content of the invention
Present invention aim to address routine lithium ion anode material specific capacity it is low the problem of, to lithium ion battery Positive electrode is modified modification, improves the chemical property of anode material for lithium-ion batteries, such as efficiency for charge-discharge, electric discharge specific volume Amount and high rate performance.
In order to achieve the above object, the invention provides a kind of new type lithium ion battery anode pole piece method of modifying, the party Method comprises the steps of：
Step 1, modification pole piece is prepared：Slurry containing the first material is formed into first coating coated in aluminium foil side, drying, obtained To modification pole piece；
Step 2, second coating will be formed in first coating of the slurry containing positive electrode active materials coated in above-mentioned modification pole piece, Drying, obtain lithium ion battery modification anode pole piece；
Wherein, the working voltage platform of first material is less than positive electrode active materials.
It is preferred that described the first material selection graphene, sulphur simple substance, cobalt acid lithium, LiFePO 4, LiMn2O4, nickel cobalt Any one in LiMn2O4, nickel cobalt lithium aluminate or two or more mixtures.
It is preferred that described positive electrode active materials selection cobalt acid lithium, LiFePO 4, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt Any one in lithium aluminate, lithium-rich manganese base material, nickel ion doped or two or more mixtures.
It is preferred that the thickness of first coating is 1 μm ~ 10 μm.
It is preferred that the thickness of second coating is 10 μm ~ 100 μm.
Present invention also offers anode slice of lithium ion battery prepared by a kind of above-mentioned method of modifying, the anode pole piece bag Containing collector, the collector is formed by aluminium foil and coated in the first coating of its side, and the is also coated with first coating Two coatings, the first coating include the first material, and the second coating includes active material, wherein, the work of the first material Voltage platform is less than positive electrode active materials.
A kind of purposes of the anode slice of lithium ion battery prepared present invention also offers above-mentioned method of modifying, wherein, The anode pole piece is used for lithium ion battery.
The present invention has advantages below：Using the lithium ion battery of present invention modification anode pole piece assembling in charge and discharge process Can shorten the transmission path of lithium ion/electronics, reduce interface impedance, bring higher efficiency for charge-discharge, specific discharge capacity with And excellent high rate performance.For example, the specific discharge capacity using the nickel cobalt aluminic acid lithium electrode of LiFePO4 modified in 0.1C Up to 194.6mAh/g, and ungroomed electrode discharge specific capacity only has 184.6mAh/g；Electric discharge of the modified electrode in 5C Specific capacity is up to 150.2mAh/g, and ungroomed electrode discharge specific capacity only has 136.2mAh/g.The lithium ion battery is just Pole pole piece method of modifying has universality, also is adapted for engineering application.
Brief description of the drawings
Fig. 1 is using first charge and discharge of the modification pole piece prepared by the embodiment of the present invention 1 as the lithium ion battery of positive pole Electric curve.
Fig. 2 is using high rate performance of the modification pole piece prepared by the embodiment of the present invention 1 as the lithium ion battery of positive pole Curve.
Fig. 3 is as the resistance before the lithium ion battery circulation of positive pole using the modification pole piece prepared by the embodiment of the present invention 1 Anti- curve.
Fig. 4 is using first charge and discharge of the modification pole piece prepared by the embodiment of the present invention 2 as the lithium ion battery of positive pole Electric curve.
Fig. 5 is the SEM scanning electron microscope (SEM) photographs of the modification anode pole piece prepared by the embodiment of the present invention 3.
Fig. 6 is using first charge and discharge of the modification pole piece prepared by the embodiment of the present invention 3 as the lithium ion battery of positive pole Electric curve.
Fig. 7 is using first charge and discharge of the modification pole piece prepared by the embodiment of the present invention 4 as the lithium ion battery of positive pole Electric curve.
Embodiment
A kind of new type lithium ion battery anode pole piece method of modifying provided by the invention comprises the steps of：
Step 1, modification pole piece is prepared：Slurry containing the first material is formed into first coating coated in aluminium foil side, drying, obtained To modification pole piece；
Step 2, second coating will be formed in first coating of the slurry containing positive electrode active materials coated in above-mentioned modification pole piece, Drying, obtain lithium ion battery modification anode pole piece；
Wherein, the working voltage platform of first material is less than positive electrode active materials.
Described first material selection graphene, sulphur simple substance, cobalt acid lithium, LiFePO 4, LiMn2O4, nickle cobalt lithium manganate, Any one in nickel cobalt lithium aluminate or two or more mixtures.
Described positive electrode active materials selection cobalt acid lithium, LiFePO 4, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, Any one in lithium-rich manganese base material, nickel ion doped or two or more mixtures.
The thickness of the first coating is 1 μm ~ 10 μm.
The thickness of the second coating is 10 μm ~ 100 μm.
Described the first material and the usage ratio of positive electrode active materials are by adjusting the thickness of first coating and second coating Degree is realized.
Technical scheme is described further below in conjunction with drawings and examples.
Embodiment 1
（1）It is 8 in mass ratio:1:1 weighs LiFePO 4 material (LiFePO4, LFP), conductive agent and binding agent, with NMP （N-Methyl pyrrolidone, 1-METHYLPYRROLIDONE）As solvent wet-mixing, coated on aluminium foil, obtained after drying Contain the pole piece of low-voltage positive electrode as modification pole piece in aluminium foil side；The conductive agent is acetylene black, and the binding agent is PVDF（Polyvinylidene Fluoride, Kynoar）；
（2）It is 8 in mass ratio:1:1 weighs positive electrode active materials nickel cobalt lithium aluminate (LiNi0.8Co0.15Al0.05O2, NCA), lead Electric agent and binding agent, using NMP as solvent wet-mixing after obtain anode sizing agent；
（3）With step（1）Manufactured modification pole piece coats one layer of step as collector on its surface（2）Manufactured positive pole slurry Material, lithium ion battery modification anode pole piece Al-LFP-NCA is obtained after drying.
Wherein, the coating of low-voltage positive electrode is contained in aluminium foil side, and thickness is 5 μm.
The coating of positive electrode active materials, thickness are 50 μm.
Using first charge-discharge curve such as figure of the modification pole piece prepared by the present embodiment 1 as the lithium ion battery of positive pole Shown in 1, discharge and recharge is carried out with 0.1C electric current, it can be seen that using its first Zhou Fang electricity ratio of the battery of Al-LFP-NCA modification positive poles Capacity is 194.6mAh/g, higher than the 184.6mAh/g of the unmodified electrodes of Al-NCA.Using its storehouse first of the battery of modification positive pole Logical sequence efficiency is 85.0%, higher than the 81.6% of unmodified electrode.
Using the high rate performance curve such as Fig. 2 of modification pole piece as the lithium ion battery of positive pole prepared by the present embodiment 1 It is shown, it can be seen that using the battery of Al-LFP-NCA modification positive poles under the big multiplying power electric currents of 5C, its specific discharge capacity 150.2mAh/g, higher than the 136.2mAh/g of the unmodified electrodes of Al-NCA.
Using the modification pole piece prepared by the present embodiment 1 as impedance diagram such as Fig. 3 before the lithium ion battery circulation of positive pole It is shown, it can be seen that to there is smaller impedance value using the Al-LFP-NCA batteries for modifying positive pole, advantageously in ion and electricity The transmission of son.
Embodiment 2
（1）It is 8 in mass ratio:1:1 weighs grapheme material (grapheme, GR), conductive agent and binding agent, using NMP as Solvent wet-mixing, coated in the pole piece for obtaining containing low-voltage positive electrode in aluminium foil side on aluminium foil, after drying as modification Pole piece；The conductive agent is acetylene black, and the binding agent is that PVDF is Kynoar；
（2）It is 8 in mass ratio:1:1 weighs positive electrode active materials nickel cobalt lithium aluminate (LiNi0.8Co0.15Al0.05O2, NCA), it is conductive Agent and binding agent, using NMP as solvent wet-mixing after obtain anode sizing agent；
（3）With step（1）Manufactured modification pole piece coats one layer of step as collector on its surface（2）Manufactured positive pole slurry Material, lithium ion battery modification anode pole piece Al-GR-NCA is obtained after drying.
The coating of low-voltage positive electrode is contained in aluminium foil side, and thickness is 5 μm.
The coating of positive electrode active materials, thickness are 50 μm.
Lithium ion battery modification anode pole piece Al-GR-NCA electrochemical property test result is as shown in figure 4, with 0.1C Electric current carry out discharge and recharge, it can be seen that use battery its specific discharge capacity of Al-GR-NCA modification positive poles as 197.6mAh/g, Higher than the 184.6mAh/g of the unmodified electrodes of Al-NCA.Meanwhile the battery of Al-GR-NCA modification positive poles, under 2C multiplying powers, it is put Electric specific capacity 165.7mAh/g, higher than the 148.7mAh/g of the unmodified electrodes of Al-NCA.This kind of pole piece method of modifying makes raw material Volumetric properties and high rate performance all be improved significantly.
Embodiment 3
（1）It is 8 in mass ratio:1:1 weighs sulfur materials (S), conductive agent and binding agent, using NMP as solvent wet-mixing, applies Apply on aluminium foil, the pole piece for obtaining containing low-voltage positive electrode in aluminium foil side after drying is as modification pole piece；The conductive agent For acetylene black, the binding agent is that PVDF is Kynoar；
（2）It is 8 in mass ratio:1:1 weighs iron phosphate serving as positive active material (LiFePO4, LFP), conductive agent and bonding Agent, using NMP as solvent wet-mixing after obtain anode sizing agent；
（3）With step（1）Manufactured modification pole piece coats one layer of step as collector on its surface（2）Manufactured positive pole slurry Material, lithium ion battery modification anode pole piece Al-S-LFP is obtained after drying.
The coating of low-voltage positive electrode is contained in aluminium foil side, and thickness is 5 μm.
The coating of positive electrode active materials, thickness are 100 μm.
SEM figures using the modification anode pole piece prepared by the present embodiment 3 are as shown in Figure 5, it can be seen that short grained phosphorus Sour iron lithium active material is covered in sulfur materials surface.
Using first charge-discharge curve such as figure of the modification pole piece prepared by the present embodiment 3 as the lithium ion battery of positive pole Shown in 6, discharge and recharge is carried out with 0.1C electric current, use its first discharge specific capacities of battery of Al-S-LFP modification positive poles for 247.2mAh/g。
Embodiment 4：
（1）By 8:1:1 weighs LiFePO 4 material (LiFePO4, LFP), conductive agent and binding agent, it is wet using NMP as solvent Method mixes, coated in the pole piece for obtaining containing low-voltage positive electrode in aluminium foil side on aluminium foil, after drying as modification pole piece；Institute It is acetylene black to state conductive agent, and the binding agent is that PVDF is Kynoar；
（2）By 8:1:1 weighs positive electrode active materials nickel cobalt lithium aluminate (LiNi0.8Co0.15Al0.05O2, NCA), conductive agent and Binding agent, using NMP as solvent wet-mixing after obtain anode sizing agent；
（3）With step（1）Manufactured modification pole piece coats one layer of step as collector on its surface（2）Manufactured positive pole slurry Material, lithium ion battery modification anode pole piece Al-LFP-NCA is obtained after drying.
The coating of low-voltage positive electrode is contained in aluminium foil side, and thickness is 2 μm.
The coating of positive electrode active materials, thickness are 10 μm.
Lithium ion battery modification anode pole piece Al-LFP-NCA electrochemical property test result as shown in fig. 7, with 0.1C electric current carries out discharge and recharge, it can be seen that use its specific discharge capacities of battery of Al-LFP-NCA modification positive poles for 190.6mAh/g, higher than the 184.6mAh/g of the unmodified electrodes of Al-NCA.
In summary, anode slice of lithium ion battery method of modifying provided by the invention, by working voltage platform less than just The low voltage material of pole active material is coated on aluminium foil, using the modification pole piece as collector, then in one layer of its surface coating Anode active material of lithium ion battery.Using lithium ion battery the depositing due to ladder potential of present invention modification anode pole piece assembling It can shorten the transmission path of lithium ion/electronics in charge and discharge process, reduce interface impedance, bring higher discharge and recharge to imitate Rate, specific discharge capacity and excellent high rate performance.The capacity through modified electrode and first effect that each embodiment obtains will be higher than The electrode capacity modified and first effect are not done, and thus provable, the present invention is effectively improved the electrochemistry of lithium ion cell positive Performance.
In addition, the anode slice of lithium ion battery method of modifying has universality, preparation method is simple, is adapted to engineering should With.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.

Claims (9)

1. a kind of new type lithium ion battery anode pole piece method of modifying, it is characterised in that the method includes the steps of：
Step 1, modification pole piece is prepared：Slurry containing the first material is formed into first coating coated in aluminium foil side, drying, obtained To modification pole piece；
Step 2, second coating will be formed in first coating of the slurry containing positive electrode active materials coated in above-mentioned modification pole piece, Drying, obtain lithium ion battery modification anode pole piece；
Wherein, the working voltage platform of first material is less than positive electrode active materials.
2. new type lithium ion battery anode pole piece method of modifying as claimed in claim 1, it is characterised in that the first described material It is any one in material selection graphene, sulphur simple substance, cobalt acid lithium, LiFePO 4, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate Kind or two or more mixtures.
3. new type lithium ion battery anode pole piece method of modifying as claimed in claim 1, it is characterised in that described positive pole is lived Property material selection cobalt acid lithium, LiFePO 4, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium-rich manganese base material, nickel mangaic acid Any one in lithium or two or more mixtures.
4. new type lithium ion battery anode pole piece method of modifying as claimed in claim 1, it is characterised in that the thickness of first coating Spend for 1 μm ~ 10 μm.
5. new type lithium ion battery anode pole piece method of modifying as claimed in claim 1, it is characterised in that the thickness of second coating Spend for 10 μm ~ 100 μm.
6. anode slice of lithium ion battery prepared by the method for modifying in a kind of 1-5 according to claim described in any one, its It is characterised by, the anode pole piece includes collector, and the collector is made up of aluminium foil and the first coating coated in its side, Second coating is also coated with first coating, the first coating includes the first material, and the second coating includes active material, Wherein, the working voltage platform of the first material is less than positive electrode active materials.
7. anode slice of lithium ion battery as claimed in claim 6, it is characterised in that described the first material selection graphite Any one or two kinds in alkene, sulphur simple substance, cobalt acid lithium, LiFePO 4, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate with On mixture.
8. anode slice of lithium ion battery as claimed in claim 6, it is characterised in that described positive electrode active materials selection cobalt It is any one in sour lithium, LiFePO 4, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium-rich manganese base material, nickel ion doped Kind or two or more mixtures.
9. the use of anode slice of lithium ion battery prepared by the method for modifying in a kind of 1-5 according to claim described in any one On the way, it is characterised in that the anode pole piece is used for lithium ion battery.
CN201710771251.3A 2017-08-31 2017-08-31 Novel lithium ion battery positive pole piece, application thereof and modification method of pole piece Active CN107785537B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710771251.3A CN107785537B (en) 2017-08-31 2017-08-31 Novel lithium ion battery positive pole piece, application thereof and modification method of pole piece

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710771251.3A CN107785537B (en) 2017-08-31 2017-08-31 Novel lithium ion battery positive pole piece, application thereof and modification method of pole piece

Publications (2)

Publication Number Publication Date
CN107785537A true CN107785537A (en) 2018-03-09
CN107785537B CN107785537B (en) 2021-04-06

Family

ID=61437836

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710771251.3A Active CN107785537B (en) 2017-08-31 2017-08-31 Novel lithium ion battery positive pole piece, application thereof and modification method of pole piece

Country Status (1)

Country Link
CN (1) CN107785537B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109560249A (en) * 2018-11-30 2019-04-02 中国科学院过程工程研究所 A kind of double-layer structure anode pole piece, and its preparation method and application
CN111554879A (en) * 2020-05-11 2020-08-18 珠海冠宇电池股份有限公司 Positive plate, manufacturing method of positive plate and battery
CN112751074A (en) * 2019-10-29 2021-05-04 北京小米移动软件有限公司 Lithium ion battery, preparation method thereof and electronic equipment

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1658413A (en) * 2004-02-17 2005-08-24 比亚迪股份有限公司 Lithium cell plus plate and its preparation method and lithium ion secondary battery
CN201153140Y (en) * 2008-02-20 2008-11-19 东莞市迈科新能源有限公司 High-safety polymer battery positive pole
CN102208598A (en) * 2011-05-12 2011-10-05 中国科学院宁波材料技术与工程研究所 Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof
CN103378352A (en) * 2012-04-25 2013-10-30 协鑫动力新材料（盐城）有限公司 Lithium ion battery positive pole piece and preparation method thereof
CN203746972U (en) * 2014-01-03 2014-07-30 邓韵 Positive electrode plate
CN103972464A (en) * 2013-01-24 2014-08-06 华为技术有限公司 Positive electrode of all-solid-state lithium battery and manufacturing method thereof, and all-solid-state lithium battery
CN104600242A (en) * 2014-12-26 2015-05-06 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery composite positive material, positive plate and lithium ion battery
CN105591073A (en) * 2014-10-23 2016-05-18 深圳华粤宝电池有限公司 A cathode material used for secondary lithium batteries and a preparing method thereof
CN106560943A (en) * 2016-08-17 2017-04-12 深圳市优特利电源有限公司 Silicon-carbon negative electrode and preparation method thereof, and lithium ion battery
CN106654169A (en) * 2016-12-31 2017-05-10 山东精工电子科技有限公司 Positive electrode plate of lithium ion battery and preparation method for positive electrode plate
CN106848326A (en) * 2017-02-15 2017-06-13 深圳市沃特玛电池有限公司 Anode pole piece and lithium ion battery
CN107112143A (en) * 2014-11-14 2017-08-29 牛津大学科技创新有限公司 Electrode structure and its manufacture method

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1658413A (en) * 2004-02-17 2005-08-24 比亚迪股份有限公司 Lithium cell plus plate and its preparation method and lithium ion secondary battery
CN201153140Y (en) * 2008-02-20 2008-11-19 东莞市迈科新能源有限公司 High-safety polymer battery positive pole
CN102208598A (en) * 2011-05-12 2011-10-05 中国科学院宁波材料技术与工程研究所 Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof
CN103378352A (en) * 2012-04-25 2013-10-30 协鑫动力新材料（盐城）有限公司 Lithium ion battery positive pole piece and preparation method thereof
CN103972464A (en) * 2013-01-24 2014-08-06 华为技术有限公司 Positive electrode of all-solid-state lithium battery and manufacturing method thereof, and all-solid-state lithium battery
CN203746972U (en) * 2014-01-03 2014-07-30 邓韵 Positive electrode plate
CN105591073A (en) * 2014-10-23 2016-05-18 深圳华粤宝电池有限公司 A cathode material used for secondary lithium batteries and a preparing method thereof
CN107112143A (en) * 2014-11-14 2017-08-29 牛津大学科技创新有限公司 Electrode structure and its manufacture method
CN104600242A (en) * 2014-12-26 2015-05-06 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery composite positive material, positive plate and lithium ion battery
CN106560943A (en) * 2016-08-17 2017-04-12 深圳市优特利电源有限公司 Silicon-carbon negative electrode and preparation method thereof, and lithium ion battery
CN106654169A (en) * 2016-12-31 2017-05-10 山东精工电子科技有限公司 Positive electrode plate of lithium ion battery and preparation method for positive electrode plate
CN106848326A (en) * 2017-02-15 2017-06-13 深圳市沃特玛电池有限公司 Anode pole piece and lithium ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109560249A (en) * 2018-11-30 2019-04-02 中国科学院过程工程研究所 A kind of double-layer structure anode pole piece, and its preparation method and application
CN112751074A (en) * 2019-10-29 2021-05-04 北京小米移动软件有限公司 Lithium ion battery, preparation method thereof and electronic equipment
CN111554879A (en) * 2020-05-11 2020-08-18 珠海冠宇电池股份有限公司 Positive plate, manufacturing method of positive plate and battery

Also Published As

Publication number Publication date
CN107785537B (en) 2021-04-06

Similar Documents

Publication Publication Date Title
CN112151764A (en) Electrode plate and preparation method and application thereof
RU2631239C2 (en) Method of producing a layer of active material of positive electrode for lithium-ion battery and layer of active material of positive electrode for lithium-ion accumulator
CN111081982A (en) Lithium ion battery lithium supplementing method
CN101281987A (en) Ferrous phosphate lithium-based polyalcohol lithium battery and method for manufacturing the same
CN114142003B (en) Composite positive electrode slurry, lithium ion secondary battery and preparation method of lithium ion secondary battery
CN108493419B (en) Temperature-sensitive composite electrode and preparation method thereof
CN109509909A (en) Secondary battery
CN111799470B (en) Positive pole piece and sodium ion battery
CN106532055A (en) Lithium ion battery binder and lithium ion battery
CN102427123A (en) Lithium ion secondary battery and anode sheet thereof
CN112614703B (en) Negative electrode material of ionic capacitor and preparation method and application thereof
CN105761944B (en) A kind of hybrid super capacitor anode composite piece and preparation method thereof, hybrid super capacitor
CN111969182A (en) Positive pole piece, preparation method thereof, and lithium ion secondary battery, electric vehicle and electronic product related to positive pole piece
CN107785537A (en) A kind of method of modifying of new type lithium ion battery anode pole piece, its purposes and pole piece
JP2000011991A (en) Organic electrolyte secondary battery
CN114094070A (en) Titanium niobate-coated hard carbon composite material and preparation method thereof
CN116454283A (en) Potassium ion battery positive electrode additive and preparation method and application thereof
CN108039453B (en) Method for improving cycle performance of negative electrode of lithium battery by using coating
CN109638233A (en) A kind of solid state ionic conductor and lithium-rich manganese base material combination electrode and lithium ion battery
CN115207335A (en) Low-temperature chargeable and dischargeable lithium ion battery cathode material and lithium ion battery
CN114784401A (en) Long-cycle-life lithium ion battery and method for prolonging cycle life of lithium ion battery
CN212365998U (en) Electrode structure of lithium solid-state battery
CN109802088B (en) Lithium ion battery capable of being quickly charged and manufacturing method thereof
CN113594418A (en) Preparation method of positive pole piece, preparation method of battery, positive pole piece and battery
CN113422027A (en) Positive electrode composite material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant