CN106935820A - A kind of manganese-based anode material and lithium titanate battery - Google Patents

A kind of manganese-based anode material and lithium titanate battery Download PDF

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Publication number
CN106935820A
CN106935820A CN201710152502.XA CN201710152502A CN106935820A CN 106935820 A CN106935820 A CN 106935820A CN 201710152502 A CN201710152502 A CN 201710152502A CN 106935820 A CN106935820 A CN 106935820A
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China
Prior art keywords
lini
manganese
lithium titanate
clad
base material
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Pending
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CN201710152502.XA
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Chinese (zh)
Inventor
孟猛
张奇
战云峰
王丽
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Shandong Weilintexin Energy Technology Co Ltd
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Shandong Weilintexin Energy Technology Co Ltd
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Priority to CN201710152502.XA priority Critical patent/CN106935820A/en
Publication of CN106935820A publication Critical patent/CN106935820A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/50—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
    • H01M4/48—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

This application discloses a kind of manganese-based anode material and lithium titanate battery, manganese-based anode material includes manganese base base material and the clad being coated on base material, and in Mn-site doping, clad includes TiO to wherein manganese base base material2、CeO2、SiO2、AlF3、NiP、Zn(OH)2Or the one kind in Graphene.The present invention is coated with coating on the positive electrode of lithium titanate battery, and is doped, and effectively increases the electric conductivity and ion diffusion rates of positive electrode, so as to high voltage, high life and safely and efficiently lithium titanate battery is obtained.

Description

A kind of manganese-based anode material and lithium titanate battery
Technical field
The present invention relates to lithium titanate battery field, specifically a kind of manganese-based anode material and lithium titanate battery.
Background technology
Lithium titanate material is a kind of high performance lithium secondary battery cathode material.During Li is embedded in or deviates from, crystal formation Do not change, Volume Changes are less than 1%, therefore are referred to as " zero strain material ", can avoid in charge and discharge cycles due to electricity Pole material stretches and causes structural damage back and forth, so as to improve the cycle performance and service life of electrode, with more negative than carbon The more excellent cycle performance in pole.
Lithium titanate is a kind of new lithium ion battery negative material, is had the characteristics that：1) charging/discharging voltage platform is high (1.55VvsLi/Li+), far above lithium current potential, so as to fundamentally prevent the formation of Li dendrite, and does not send out with electrolyte Raw reaction；2) deformation is small and be referred to as " zero strain material " in itself during discharge and recharge, drastically increases battery cyclicity in itself Energy and security performance；3) surface does not form diaphragm, and efficiency for charge-discharge is high；4) lithium ion mobility speed is high, high current charge-discharge Ability is good；5) low temperature charge-discharge performance is good.
Graphene (Graphene) is a kind of new material of the individual layer laminated structure being made up of carbon atom.It is a kind of former by carbon Son is with the flat film that sp2 hybridized orbits composition hexangle type is in honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness.Stone Black alkene be in the world it is most thin be but also most hard nano material, it is almost fully transparent, only absorb 2.3% light；Heat conduction Coefficient is up to 5300W/mK, and higher than CNT and diamond, its electron mobility is more than 15000cm under normal temperature2/ Vs, It is again higher than CNT or silicon crystal, and resistivity only about 10-6 Ω cm, it is lower than copper or silver, it is minimum world resistivity Material.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, therefore is expected to can be used to develop thinner, conductive speed The faster a new generation's electronic component of degree or transistor.
The content of the invention
It is an object of the invention to provide a kind of manganese-based anode material and lithium titanate battery, so that positive electrode can be improved Electric conductivity and ion diffusion rates.
The object of the present invention is achieved like this：A kind of manganese-based anode material, including manganese base base material and be coated on base material Clad, wherein manganese base base material in Mn-site doping, the element of Mn-site doping include one kind in Ni, Fe, V, Al, Mg or Co or Several, clad includes TiO2、CeO2、SiO2、AlF3、NiP、Zn(OH)2Or the one kind in Graphene.
Further, method for coating includes sol-gel process, the precipitation method, chemical plating, hydro-thermal method and/or high temperature solid state reaction Method.
Preferably, the clad is Graphene, and the number of plies of cladding is 5-12 layers.
Wherein the material of Mn-site doping Ni and Co includes LiNi0.6Co0.2Mn0.2O2、LiNi0.33Co0.33Mn0.33O2、 LiNi0.5Co0.3Mn0.2O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2；The material of Mn-site doping Al includes LiMn1.9Al0.1O4、LiNi0.35Mn1.5Al0.15O4、LiNi0.5Mn1.42Al0.08O4Or LiNi0.45Mn1.45Al0.1O4。
A kind of lithium titanate battery, including positive electrode and negative material, negative material include lithium titanate, and positive electrode includes Manganese base base material and the clad being coated on base material, wherein manganese base base material in Mn-site doping, the element of Mn-site doping include Ni, One or more in Fe, V, Al, Mg or Co, clad includes TiO2、CeO2、SiO2、AlF3、NiP、Zn(OH)2Or Graphene In one kind.
Further, method for coating includes sol-gel process, the precipitation method, chemical plating, hydro-thermal method and/or high temperature solid state reaction Method.
Preferably, the clad is Graphene, and the number of plies of cladding is 5-12 layers.
Wherein the material of Mn-site doping Ni and Co includes LiNi0.6Co0.2Mn0.2O2、LiNi0.33Co0.33Mn0.33O2、 LiNi0.5Co0.3Mn0.2O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2；The material of Mn-site doping Al includes LiMn1.9Al0.1O4、LiNi0.35Mn1.5Al0.15O4、LiNi0.5Mn1.42Al0.08O4Or LiNi0.45Mn1.45Al0.1O4；
The advantage of the invention is that：
1st, the power supply platform of lithium titanate battery of the invention is in 3V-4.55V, effectively increase lithium titanate battery voltage and It is safe and efficient；
2nd, positive electrode is doped, the very big electric conductivity and ion diffusion rates that must improve lithium titanate battery；
3rd, coated using Graphene, improve the conductive speed and energy density of lithium titanate battery.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of lithium titanate battery with Mn-based material as positive pole, wherein positive pole include manganese base base material and are coated on base material Clad, the manganese base base material is LiNi0.6Co0.2Mn0.2O2, clad is Graphene.
It is prepared by negative plate：Cathode size is according to lithium titanate：Conductive charcoal (Super-P)：Electrically conductive graphite (KS6)：Bonding agent (PVDF)=92：2：1.5：3 part by weight are blended in nmp solvent, are stirred, and obtain cathode size；Slurry is applied Cloth, roll-in, vermicelli, punching obtain negative plate.
It is prepared by positive plate：Cathode size according to coated graphite alkene LiNi0.6Co0.2Mn0.2O2：Conductive charcoal (Super-P)： Electrically conductive graphite (KS6)：Bonding agent (PVDF)=95：1.5：1.5：3 part by weight are blended in nmp solvent, are stirred, and are obtained Cathode size；Slurry is coated, roll-in, vermicelli, punching obtain negative plate.
It is prepared by electrolyte：Electrolyte includes electrolyte and electrolyte solvent, wherein, electrolyte solvent is organic carbonate One or more of class, organic carboxyl acid esters, fluorination esters, ethers, sulfone class；Electrolyte is LiPF6、LiBF4、LiClO4、 LiAsO6、Li(CF3SO2)2N、LiCF3SO3In one or more.
The preparation of lithium ion battery：Negative plate, positive plate and barrier film are assembled into battery core in order, are encapsulated with aluminium plastic membrane Battery, and leave liquid injection port.Then electrolyte is irrigated from liquid injection port, encapsulation is aging.
Embodiment 2
A kind of lithium titanate battery with Mn-based material as positive pole, wherein positive pole include manganese base base material and are coated on base material Clad, the manganese base base material is LiNi0.5Co0.3Mn0.2O2, clad is Graphene.
It is prepared by negative plate：Cathode size is according to lithium titanate：Conductive charcoal (Super-P)：Electrically conductive graphite (KS6)：Bonding agent (PVDF)=92：2：1.5：3 part by weight are blended in nmp solvent, are stirred, and obtain cathode size；Slurry is applied Cloth, roll-in, vermicelli, punching obtain negative plate.
It is prepared by positive plate：Cathode size according to coated graphite alkene LiNi0.5Co0.3Mn0.2O2：Conductive charcoal (Super-P)： Electrically conductive graphite (KS6)：Bonding agent (PVDF)=95：1.5：1.5：3 part by weight are blended in nmp solvent, are stirred, and are obtained Cathode size；Slurry is coated, roll-in, vermicelli, punching obtain negative plate.
It is prepared by electrolyte：Electrolyte includes electrolyte and electrolyte solvent, wherein, electrolyte solvent is organic carbonate One or more of class, organic carboxyl acid esters, fluorination esters, ethers, sulfone class；Electrolyte is LiPF6、LiBF4、LiClO4、 LiAsO6、Li(CF3SO2)2N、LiCF3SO3In one or more.
The preparation of lithium ion battery：Negative plate, positive plate and barrier film are assembled into battery core in order, are encapsulated with aluminium plastic membrane Battery, and leave liquid injection port.Then electrolyte is irrigated from liquid injection port, encapsulation is aging.
Embodiment 3
A kind of lithium titanate battery with Mn-based material as positive pole, wherein positive pole include manganese base base material and are coated on base material Clad, the manganese base base material is LiNi0.5Mn1.42Al0.08O4, clad is Graphene.
It is prepared by negative plate：Cathode size is according to lithium titanate：Conductive charcoal (Super-P)：Electrically conductive graphite (KS6)：Bonding agent (PVDF)=91：2：1：3 part by weight are blended in nmp solvent, are stirred, and obtain cathode size；Slurry is coated, Roll-in, vermicelli, punching obtain negative plate.
It is prepared by positive plate：Cathode size according to coated graphite alkene LiNi0.5Mn1.42Al0.08O4：Conductive charcoal (Super-P)： Electrically conductive graphite (KS6)：Bonding agent (PVDF)=95：3：1：3 part by weight are blended in nmp solvent, are stirred, and obtain negative pole Slurry；Slurry is coated, roll-in, vermicelli, punching obtain negative plate.
It is prepared by electrolyte：Electrolyte includes electrolyte and electrolyte solvent, wherein, electrolyte solvent is organic carbonate One or more of class, organic carboxyl acid esters, fluorination esters, ethers, sulfone class；Electrolyte is LiPF6、LiBF4、LiClO4、 LiAsO6、Li(CF3SO2)2N、LiCF3SO3In one or more.
The preparation of lithium ion battery：Negative plate, positive plate and barrier film are assembled into battery core in order, are encapsulated with aluminium plastic membrane Battery, and leave liquid injection port.Then electrolyte is irrigated from liquid injection port, encapsulation is aging.
Embodiment 4
A kind of lithium titanate battery with Mn-based material as positive pole, wherein positive pole include manganese base base material and are coated on base material Clad, the manganese base base material is LiMn1.9Al0.1O4, clad is Graphene.
It is prepared by negative plate：Cathode size is according to lithium titanate：Conductive charcoal (Super-P)：Electrically conductive graphite (KS6)：Bonding agent (PVDF)=91：2：1：5 part by weight are blended in nmp solvent, are stirred, and obtain cathode size；Slurry is coated, Roll-in, vermicelli, punching obtain negative plate.
It is prepared by positive plate：Cathode size according to coated graphite alkene LiMn1.9Al0.1O4：Conductive charcoal (Super-P)：It is conductive Graphite (KS6)：Bonding agent (PVDF)=95：3：1：3 part by weight are blended in nmp solvent, are stirred, and obtain negative pole slurry Material；Slurry is coated, roll-in, vermicelli, punching obtain negative plate.
It is prepared by electrolyte：Electrolyte includes electrolyte and electrolyte solvent, wherein, electrolyte solvent is organic carbonate One or more of class, organic carboxyl acid esters, fluorination esters, ethers, sulfone class；Electrolyte is LiPF6、LiBF4、LiClO4、 LiAsO6、Li(CF3SO2)2N、LiCF3SO3In one or more.
The preparation of lithium ion battery：Negative plate, positive plate and barrier film are assembled into battery core in order, are encapsulated with aluminium plastic membrane Battery, and leave liquid injection port.Then electrolyte is irrigated from liquid injection port, encapsulation is aging.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate the application example, and simultaneously The non-restriction to implementation method.For those of ordinary skill in the field, can also do on the basis of the above description Go out the change or variation of other multi-forms.There is no need and unable to be exhaustive to all of implementation method.And thus drawn Obvious change that Shen goes out or among changing still in the protection domain of the application type.

Claims (9)

1. a kind of manganese-based anode material, it is characterised in that including manganese base base material and the clad being coated on base material,
The manganese base base material in Mn-site doping, the element of the Mn-site doping include one kind in Ni, Fe, V, Al, Mg or Co or It is several,
The clad includes TiO2、CeO2、SiO2、AlF3、NiP、Zn(OH)2Or the one kind in Graphene.
2. a kind of manganese-based anode material according to claim 1, it is characterised in that the method for coating includes colloidal sol-solidifying Glue method, the precipitation method, chemical plating, hydro-thermal method and/or high-temperature solid phase reaction method.
3. a kind of manganese-based anode material according to claim 1, it is characterised in that the clad is Graphene, described The number of plies of graphene coated is 5-12 layers.
4. a kind of manganese-based anode material according to claim 1 or 3, it is characterised in that the Mn-site doping Ni's and Co Material includes LiNi0.6Co0.2Mn0.2O2、LiNi0.33Co0.33Mn0.33O2、LiNi0.5Co0.3Mn0.2O2、LiNi0.8Co0.15Al0.05O2 Or LiNi0.8Co0.1Mn0.1O2。
5. a kind of manganese-based anode material according to claim 1 or 3, it is characterised in that the material of the Mn-site doping Al Including LiMn1.9Al0.1O4、LiNi0.35Mn1.5Al0.15O4、LiNi0.5Mn1.42Al0.08O4Or LiNi0.45Mn1.45Al0.1O4。
6. a kind of lithium titanate battery, including positive electrode and negative material, it is characterised in that the negative material includes metatitanic acid Lithium, the positive electrode includes manganese base base material and the clad being coated on base material,
The manganese base base material in Mn-site doping, the element of the Mn-site doping include one kind in Ni, Fe, V, Al, Mg or Co or It is several,
The clad includes TiO2、CeO2、SiO2、AlF3、NiP、Zn(OH)2Or the one kind in Graphene.
7. a kind of lithium titanate battery according to claim 6, it is characterised in that the clad is Graphene, the stone The number of plies of black alkene cladding is 5-12 layers.
8. a kind of lithium titanate battery according to claim 6 or 7, it is characterised in that the material of the Mn-site doping Ni and Co Material includes LiNi0.6Co0.2Mn0.2O2、LiNi0.33Co0.33Mn0.33O2、LiNi0.5Co0.3Mn0.2O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2。
9. a kind of lithium titanate battery according to claim 6 or 7, it is characterised in that the material bag of the Mn-site doping Al Include LiMn1.9Al0.1O4、LiNi0.35Mn1.5Al0.15O4、LiNi0.5Mn1.42Al0.08O4Or LiNi0.45Mn1.45Al0.1O4。
CN201710152502.XA 2017-03-15 2017-03-15 A kind of manganese-based anode material and lithium titanate battery Pending CN106935820A (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN108011074A (en) * 2017-10-31 2018-05-08 合肥国轩高科动力能源有限公司 A kind of pole piece preparation method for improving lithium titanate battery security performance
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CN111276687B (en) * 2018-12-04 2022-10-14 中国科学院上海硅酸盐研究所 High-voltage composite positive electrode material of lithium ion battery and preparation method and application thereof

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Application publication date: 20170707