CN105006547B - The method for coating of lithium ion battery and its electrode active material - Google Patents
The method for coating of lithium ion battery and its electrode active material Download PDFInfo
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- CN105006547B CN105006547B CN201510460476.8A CN201510460476A CN105006547B CN 105006547 B CN105006547 B CN 105006547B CN 201510460476 A CN201510460476 A CN 201510460476A CN 105006547 B CN105006547 B CN 105006547B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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 kind of lithium ion battery and its method for coating of electrode active material, it is related to and an organic layer is added to electrode material surface in a manner of chemical graft.This method includes being carbonized to the organic layer, and forms doping carbon-coating in electrode material surface in a manner of being chemically bonded.Dopant included in doping carbon-coating can react with the harmful side product formed in lithium ion battery charge and discharge process, so as to guard electrode material.In addition, the dopant included in doping carbon-coating can improve the electric conductivity of doping carbon-coating.The invention also discloses a kind of lithium ion battery, contain the doping carbon-coating in a manner of being chemically bonded on its electrode material.Dopant included in doped carbon can react with the noxious products that electrolyte decomposition is formed in lithium ion battery charge and discharge process.Included in doping carbon-coating in dopant improve electric transmission rate, so as to improve electrode material and made of the electrode material electrode electric conductivity.
Description
【Related application】
This application claims the priority of U.S. Provisional Application 62/030936, the U.S. Provisional Application is on July 30th, 2014
Entitled " the METHOD OF MAKING POROUS COATING ON ELECTRODE MATERIALS FOR LITHIUM submitted
ION BATTERIES ", the disclosure of which are incorporated by reference into the application.
【Technical field】
The present invention relates to field of batteries, more particularly to by providing new clad and coating technology with guard electrode material
With increase lithium ion battery electrode conductivuty and improve performance of lithium ion battery.
【Background technology】
Many modern comforts are required for battery as mobile electric energy.Because the packaged type energy, it is necessary to the equipment of electric energy such as
Computer, flashlight, wrist-watch and miscellaneous equipment can are portable.Even when battery is not the main energy of an equipment
During source, but the equipment still may require that battery.For example, most of automobiles are to provide major impetus by burns gasoline,
But these automobiles still need a battery, so that the engine start of automobile.Because the concern to environment, automobile is now
Gradually battery is used to replace gasoline as main power source.Therefore, battery and battery technology become increasingly prevalent with it is important.
There are various types of rechargeable batteries on the market.The basic conception of rechargeable battery is exactly them reversibly by chemical energy
Be converted to the electrochemical cell of electric energy.Each battery unit has a positive terminal (positive pole), and electronics passes through from the positive terminal
An external circuit is crossed, flows to a negative pole end (negative pole).Electronics displacement produces electric current.Can be to be connected to positive pole and bear
Device between pole provides electric current.
Because lithium ion battery has certain advantage than other types rechargeable battery, they are becoming increasingly popular,
It is widely used in the equipment such as mobile phone, computer and electric automobile.Fig. 1 shows the lithium ion battery 10 of prior art
And its operation principle.The primary clustering of lithium ion battery 10 includes negative pole 100, positive pole 101, electrolyte 102 and barrier film 103.
Barrier film 103 is used as separating negative pole 100 and positive pole 101, so as to prevent the short circuit between negative pole 100 and positive pole 101.
Positive pole 101 is typically cobalt acid lithium；Negative pole 100 is typically graphite or tin-based material.In the charging process of lithium ion battery 10, lithium from
Son can be discharged into electrolyte 102 from positive pole 101, then move to negative pole 100, i.e., from Fig. 1 left side to Fig. 1 the right.Electricity
Son is also spontaneously moved to negative pole 100 from positive pole 101 by an external circuit.In discharge process, in the lithium of negative pole 100
Ion and electrons are moved to positive pole 101 from negative pole 100, i.e., from Fig. 1 the right to Fig. 1 left side.For filling for lithium ion battery
Electricity and discharge process, the movement of lithium ion and electronics between negative pole and positive pole is critically important.
In the art, it would be desirable to produce the lithium ion battery with high-energy-density.In view of it is close to pursue high-energy
Degree, electrode material (negative material and positive electrode) has become an important focus areas because they to improve lithium from
The energy density of sub- battery significantly affects.Except energy density, electrode material also determine to a considerable extent lithium from
The capacity of sub- battery.
Table 1 shows as some of negative active core-shell material and positive electrode active materials typical materials and its their own led
Electric rate.As it can be seen from table 1 compared with carbon material, the typical negative electrode material of some in lithium ion battery and elder generation
The conductance for entering positive electrode material is at a fairly low.
Table 1
| Active material | Negative pole/positive pole | Conductance (S/cm) |
| Cobalt acid lithium LiCoO2 | Negative pole | 2.0×10-1 |
| LiFePO4 LiFePO4 | Negative pole | 1.9×10-9 |
| Silica SiO2 | Positive pole | 1.0×10-11 |
| Tin ash SnO2 | Positive pole | 1.0×10-3 |
| Carbon Carbon | N/A | 1.0×104 |
From table 1 it follows that the chemical formula of positive electrode shows, lithium (Li) is one of key element of positive electrode.
Table 1 also shows that negative material can be metal oxide.
In the running of lithium ion battery 10, when being worked more than high voltage 4.8V, electrolyte 102 is according to followingization
Learn reaction equation to decompose, LiPF therein6It is the major solute of electrolyte, is widely used in lithium ion battery：
LiPF6+H2O→LiF+POF3+2HF (1)
Decomposition reaction occurs in charge/discharge process, can form hydrogen fluoride (HF).In turn, hydrogen fluoride can corrode
(reacting therewith) cobalt acid lithium negative pole 101：
4HF+LiCoO2→LiF+CoF3+2H2O (2)
Chemical equation (2) shows that cobalt element forms cobalt trifluoride (CoF from positive pole dissolution3).Cobalt trifluoride is in electricity
Solve in liquid.Cobalt is from positive pole dissolution and is discharged into electrolyte, positive electrode is disintegrated, and cause battery performance to deteriorate.
The Surface coating of electrode material is that solve electrode material dissolving (accessory substance being harmful to i.e. in charge/discharge process)
One effective ways.In the prior art, the preparation technology including complexity the shortcomings that cladding, one pack system cladding and non-homogeneous bag
Cover.Many ripe method for coating include sol-gel process, ball-milling method, wet-mix process, chemical vapor deposition, spray pyrolysis,
Electrostatic spinning and hydro-thermal method, they have higher preparation cost and higher energy expenditure.Most of Surface coatings are at present
One-component layer, in charge/discharge process can not effectively guard electrode material from dissolution.
For example, there is the surface coating layer that trial uaes carbon as electrode material.But because carbon is inert component, it is just
Can not effectively guard electrode material from chemical dissolution.Carbon can provide the interim screen between HF and electrode material at most
Barrier.If carbon is porous, hydrogen fluoride in the solution is eventually directly contacted with electrode and erosion electrode material.Solve lithium from
Another method of sub- battery electrode material metal dissolving problem is to use metal oxide to occur as sacrifice agent with HF anti-
Should.But metal oxide is used on clad, the resistivity of electrode material will be significantly improved.
The method of electrode-clad also has a problem to be at present, and the clad of gained is typically uneven.Particularly work as
When using physical method, for example ball-milling method, spray pyrolysis are to prepare these clads, it will usually it is uneven coating thickness occur
The problem of.The part of relative thin is its weak spot in non-homogeneous clad, goes directly to connect to HF because they can provide chance
Touch active material and react therewith.
The quality of electrode material clad, structure and feature are extremely important to battery performance.Therefore, led in battery manufacture
In domain, always it is desirable to improve the clad of battery electrode.
【The content of the invention】
The present invention relates to protection battery electrode material devices, systems, and methods, there is provided a sacrifice agent be used for in battery
It is corrosive caused by charge and discharge process or harmfulness accessory substance reacts.Embodiments of the invention can apply in height
The lithium ion battery with high energy density to be worked under voltage conditions.The sacrifice agent can be located in clad, and it can not only improve bag
The electric conductivity of coating, and can be by being chemically bonded to obtain mode guard electrode active material.
In an embodiment of the present invention, a dopant is provided in by the clad of protection component material (such as electrode),
As sacrifice agent.Sacrifice agent can be metal or metalloid.For example, in embodiment, corrosive byproducts are hydrogen fluoride, electrode
Metalic contamination or metalloid dopant in material clad can consume hydrogen fluoride.By this way, hydrogen fluoride can not be with
Electrode material directly contacts, so as to prevent the metal dissolving of electrode material.In other words, the dopant in clad is as electrode material
The protective agent of material, prevent corrosion function of the caused corrosive byproducts to electrode material in charge and discharge process.
The present embodiments relate to the electrode material clad of lithium ion battery, the material is mainly carbon.Carbon can be co-doped with
It is miscellaneous to have metal or metalloid, to provide a sacrifice agent.In addition, carbon can also be different from the chemical combination of carbon doped with its valent state
The nonmetalloid of valence state (the such as larger than valent state of carbon or more than one predetermined threshold value) (such as nitrogen, the phosphorus of+5 valencys).In carbon
The middle nonmetalloid (such as the nitrogen or phosphorus of+5 valencys) for adulterating its valent state and being different from the valent state of carbon, can improve carbon coating
The electric conductivity of layer.It is not pure carbon although coating layer material is mainly carbon, so by this way by the use of carbon as clad, can
To be considered complex function clad.According to embodiments of the present invention, carbon coating layer also includes other materials as dopant, such as gold
Category, metalloid, nitrogen, phosphorus or combinations thereof.These dopants may be from the organic compound with functional group.It will organise
Compound is used to react to form auto-dope clad, the erosion that it can be with guard electrode material from side reaction, and improves electrode
The electric conductivity of active material.
Except the characteristic for coating layer material, the present invention also proposes a kind of side for being coated the coating layer material
Method, it make use of the chemical bonding between coating layer material and electrode material.Therefore, the embodiment of the invention discloses by that will mix
The method that miscellaneous carbon geochemistry is bonded to electrode material surface and is coated on battery electrode material.This can include：By an organic layer
First is chemically bonded on electrode material, and the organic layer then is converted into doping carbon-coating.The embodiment of the present invention includes an electricity
Pond, its electrode material chemical bonding have doped carbon.
The foregoing feature and technical advantage for quite widely having summarised the present invention, it is following so as to more fully understand
The detailed description of the present invention.The further feature and advantage of the present invention will later be described, and it forms the claims in the present invention
Theme.Those skilled in the art are it will be noted that one easily can be used as by the use of the concept and specific embodiment disclosed
Basis, for changing or being designed to perform the other structures of the identical purpose of the present invention.Those skilled in the art also should be appreciated that
Arrive, the spirit and scope of the invention that this equivalent constructions illustrate without skew in accessory claim.It is counted as spy of the invention
Property novel features, about its tissue and operation method, together with other purposes and advantage, from following description with reference to the accompanying drawings
Can preferably it be understood.However, it should profoundly recognize, each accompanying drawing is used only as describing and illustrated provided herein
Purposes, it is not intended to the definition as the limitation present invention.
【Brief description of the drawings】
For a more complete understanding of the present invention, embodiments of the invention are described referring now to the following drawings, wherein：
Fig. 1 shows the lithium ion battery and its operation principle of a prior art.
Fig. 2 shows a process of the embodiment of the present invention.
Fig. 3 shows a process of the embodiment of the present invention.
Fig. 4 shows a process of the embodiment of the present invention.
Fig. 5 shows the clad electrode material of the embodiment of the present invention.
Fig. 6 shows the lithium ion battery of the embodiment of the present invention.
The transmission electron microscope image of electrode material before and after the cladding of Fig. 7 A and 7B the display embodiment of the present invention.
(solid) and the high-resolution Li of (hollow) afterwards before Fig. 8 A display claddings1.2Mn0.6Ni0.2O2(lithium-rich anode
Material, LRCM) Si2p x-ray photoelectron power spectrum (XPS).
(solid) and the high-resolution Li of (hollow) afterwards before Fig. 8 B display claddings1.2Mn0.6Ni0.2O2(lithium-rich anode
Material, LRCM) N1s x-ray photoelectron power spectrum (XPS).
Electrochemical impedance spectroscopy (EIS) curve map of electrode material before and after the cladding of Fig. 9 display embodiment of the present invention.
Figure 10 shows a process of the embodiment of the present invention.
It should be appreciated that accompanying drawing is not necessarily drawn to scale, the disclosed embodiments are display schematic diagram and part sometimes
View.In some cases, some details for not influenceing to understand the present invention can be omitted.It is it will of course be appreciated that of the invention and unlimited
In described specific embodiment.
【Embodiment】
Lithium ion battery with high working voltage is advantageous in this area.But with (such as 4.8 volts of high voltage
It is special or higher) lithium ion battery of work, its battery electrode active material can corrode.As described above, lithium ion battery exists
The decomposition of electrolyte can be caused during discharge and recharge, corrosive hydrogen fluoride can be produced.As described above, hydrogen fluoride can be to electrode activity
Material causes damage.For example, hydrogen fluoride can be with cobalt acid lithium LiCoO2React, and cobalt element is discharged into electricity from electrode material
Solve in liquid.
During seeking to solve the problem (such as hydrogen fluoride reacts with lithium ion battery electrode material), inventor
Recognize, the material for electrode material clad that prevent electrode from being reacted with harmful side product (HF), one of them
Consideration is whether the coating layer material has high conductivity.Another consideration factor is electrode-clad layer material and with electrode material
The overall conductivity of the electrode of manufacture.In some cases, it is desired to can manufacture its electrode has high conductivity (low-resistivity)
Battery.
The embodiment of the present invention provides a kind of sacrifice agent or scavenger, for avoiding electrode material from having with what is formed in battery
Evil property or corrosive accessory substance react.So as to Corrosive Materia such as hydrogen fluoride, would not directly occur with electrode material
React and cause electrode material to corrode.The embodiment of the present invention also provides the sacrifice agent around electrode material surface.For example, it can carry
For a protective layer so that the protective layer can set barrier together between corrosion products and electrode material.The protective layer
Can also be configured such that sacrifice agent be centered around around electrode material or on the surface of electrode material, or both have concurrently, so as to
Reacted with harmfulness or corrosive byproducts.Above-mentioned protective layer can also be used to increase electric conductivity so that guard electrode material
While material but not improve the overall resistivity of electrode material and electrode.In addition, protective layer can be by being chemically bonded mode
It is coated on electrode material.
Fig. 2 shows a process 20 of the embodiment of the present invention.Process 20 is to provide to protect and improve for lithium ion cell electrode
The electric conductivity of lithium ion cell electrode.Process 20 starts from step 200, and lithium ion is provided using manufacture method known in the art
The material of battery.Step 200 can provide the material of battery component, such as electrode (negative pole and positive pole), electrolyte and diaphragm (class
It is similar to element shown in Fig. 1 lithium ion battery 10).In step 201, there is provided electrode material have a kind of sacrifice agent, in electrode material
In the clad of material, (such as charging/putting for being reacted with the corrosive byproducts formed during lithium ion battery works
The corrosive byproducts formed during electric process).Step 202 configures coating layer material to improve its electric conductivity.It will be noted that
Step 201 and step 202 can occur simultaneously.In the electrode-clad layer material of step 203, including sacrifice agent, it is used to manufacture
One or more electrodes.
For example, electrode (such as negative pole) can include 94% Li containing clad by one kind1.2Mn0.6Ni0.2O2(lithium-rich anode
Material, LRCM), 3% acetylene carbon black and 3% Kynoar (PVDF) be scattered in the slurry of 1-METHYLPYRROLIDONE (NMP) solvent
Material is made.This slurry can be uniformly coated on aluminium foil (current collector) by a kind of coating device, and by true under the conditions of 120 degree
Sky is dried 12 hours, so as to form electrode.Except the electrode material that cladding described here is formed, above-mentioned electrode material and other
Component such as electrolyte, diaphragm etc., it can be assembled into lithium ion battery to form a kind of lithium-ion electric similar to shown in Fig. 1
Pond.
Fig. 3 shows the process 30 of the embodiment of the present invention.Process 30 is to provide to protect and improve lithium for lithium ion cell electrode
The electric conductivity of ion battery electrode.Process 30 starts from step 300, and lithium-ion electric is provided using preparation method known in the art
The active component of pond electrode.The other materials of lithium ion battery can also be equally provided.This material can include electrolyte and
Diaphragm (is similar to the element shown in Fig. 1 lithium ion batteries).Electrode active material can be inorganic, metal oxide (MO), metal
Phosphate, metal sulfide or its combination.Electrode active material can be inorganic, metal oxide and metal phosphate such as
LiCoO2、LiNiO2、LiMn2O4、LiFePO4And SnO2.In Fig. 4, shown electrode active material 40 be shown as one it is spherical, but
It can also be any shape.In embodiments of the invention, electrode active material can be Li1.2Mn0.6Ni0.2O2(lithium-rich anode
Material) nano particle, particle diameter about 200nm.
Process 30 is reacted by chemical graft and then carbonisation is used for lithium ion cell electrode material to provide one kind
The doping carbon coating layer of material.Chemical graft reacts and carbonisation will be described in step 301-304.In step 301, electricity
Pole active material 40 is reacted with a kind of solution containing additive, and electrode active material 40 is pre-processed with protonation.According to this
Inventive embodiments, it is surface protonated to react the step 401 for being shown in Fig. 4.Additive solution can be weakly acidic solution, such as any
A kind of acetic acid, oxalic acid, formic acid and citric acid are in any organic solvent such as isopropanol, methanol, ethanol, isopropanol or acetone
In, or its combination.Surface protonated reaction produces one or more functional groups on electrode active material 40.So as to electrode active
The surface of property material 40 is covered by hydroxyl.Hydrogen ion in acid carries out anti-with the Surface Oxygen of metal oxide or metal phosphate
Should, so as to form the surface of a protonation.As shown in step 401, electrode active material 40 forms chemical bond, makees with hydrogen ion
With the electrode active material 41 (protonation metal oxide or protonation metal phosphate) for forming protonation.Electrode active material
Can include metal oxide, metal phosphate, metal sulfide, for similar material of the lithium ion battery as active material
Material or its combination.Compared with the method for other jacketed electrode active materials, the formation of above-mentioned chemical bond has larger in this area
Advantage, this can be described below.
Step 302 is a kind of chemical graft reaction, as described in step 402, wherein the protonation (proton of electrode active material 41
Change metal oxide or protonation metal phosphate) reacted with a kind of organic metal additive.So as to metal/metalloid
Atom is introduced in the organic coating layer of electrode active material 40.Organic metal additive can have a reactive functionality R1
(such as epoxide group), an alkoxy grp R-O- and metallic atom or metalloid atom (such as titanium, aluminium, silicon, tin, magnesium, zinc,
Zirconium, and combinations thereof).Organic metal additive can include silane, aluminium, titanium, zirconium, and combinations thereof be used as coupling agent.Coupling
Agent can include functional group such as epoxy radicals, alkoxy and amine, including (ethylenediamine base-N- ethyoxyls) titanate esters of isopropoxy three and
3- glycydoxy trimethoxy silanes, and combinations thereof.
In the chemical graft reaction of step 402, organic metal additive and the protonation (protonation of electrode active material 41
Metal oxide or protonation metal phosphate) protonation surface reacted, to produce the electrode activity of organic coating layer
Material 42 and an accessory substance R-OH.Therefore, in step 402, protonation surface is with organic metal additive in electrode activity
Material 40 (metal oxide or metal phosphate) surface react it is upper formation the first Coated with Organic Matter layer.The organic matter layer will
Electrode active material 40 envelopes.The hydrogen on protonation surface reacts with R-O groups, can form accessory substance R-OH.Organic bag
Coating electrode active material 42 is to surround (the metal oxidation of electrode active material 40 by the organic layer of metallic atom or metalloid atom
Thing or metal phosphate).Metallic atom or metalloid atom are chemically bonded to the appearance of metal oxide or metal phosphate
On face.
In step 303, there is the reaction of another chemical graft, it adds the second organic layer on electrode active material 40 (one
Individual organic layer is added on the electrode active material 42 of organic coating layer), as described in step 403.Implementation according to the present invention
Example, in chemical graft reaction, the electrode active material 42 and one of organic coating layer is rich in the organic compound of nitrogen carbon
React, to form the electrode active material 43 (metal oxide of two layers of organic coating layer) of two layers of organic coating layer.This
Outside, according to the embodiment of the present invention, reacted in the chemical graft, the electrode active material 42 of organic coating layer is with being rich in phosphorus carbon
Organic compound chemically react, with formed two layers of organic coating layer (two layers of the organic coating layer of electrode active material 43
Metal phosphate).In addition, according in the embodiment of the present invention, reacted in the chemical graft, the electrode activity material of organic coating layer
Material 42 is reacted with the organic compound of (1) rich in nitrogen carbon and the organic compound of (2) rich in phosphorus carbon, to be formed
Electrode active material 43 (metal oxide of two layers organic coating layer and the gold of two layers of organic coating layer of two layers of organic coating layer
Belong to phosphate).Step 403 shows R2- X is as the organic compound rich in nitrogen carbon or the organic compound rich in phosphorus carbon
Thing.X is nitrogen (or phosphorus) doping and carbon.Except nitrogen and carbon, the also functional functional group R of the compound2。
Due to R1And R2Between chemical reaction, the compound R of introducing2- X is grafted on organic coating layer metal oxide.
Therefore, if R1It is epoxy radicals, R2Can be amido, vice versa (i.e. if R1It is amido, R2Can be epoxy radicals).R2- X can
To be melamine.Electrode active material 40 (metal oxide or metal phosphate), by the two chemical graft steps, quilt
Coat two layers of organic material.
In the embodiment of the present invention, one organic compound rich in phosphorus carbon of step 303 introducing to organic coating layer,
As described in step 403.Nitrogen is auto-dope agent, because nitrogen-atoms is the presoma for adulterating carbon coating layer-organic coating layer.That is, nitrogen
Atom has been present in compound, and organic clad is formed for reacting.So, without from organic layer or doping carbon coating layer
Nitrogen-atoms is incorporated into doping carbon coating layer by outer some other sources.Introduced nitrogen into from another source to carbon coating layer
It is interior, obtain a coating layer material containing N doping including the use of ammonia.Therefore, in coating layer material, according to the present invention
Embodiment, nitrogen is the auto-dope agent from nitrogen-enriched compounds.Nitrogen may originate from for organic coating layer electrode active material
42 melamines to react.Nitrogen and carbon source may be from：Melamine, polyethylene Asia amine, polyacrylamide, pyrroles and its
Combination.
In embodiments of the invention, the compound rich in phosphorus carbon is included in the reaction of step 403.Phosphorus is to mix certainly
Miscellaneous dose, because phosphorus atoms are the presomas for adulterating carbon coating layer-organic coating layer.I.e. phosphorus atoms have been present in compound, use
Organic clad is formed in reaction.So, it is without some other sources outside organic layer or doping carbon coating layer that phosphorus is former
Son is incorporated into doping carbon coating layer.
In step 304, organic coating layer (has two layers), can be through Overheating Treatment-carbonisation, as described in step 404.Carbonization
Process can about 400-1200 DEG C temperature and carried out in following any air：Argon gas, helium, nitrogen, hydrogen,
Carbon dioxide or its composition.In step 404, two organic layers (polymeric layer) are carbonized by the heat of application.In step 404
In carbonisation, organic (polymer) material is converted into codope carbon material, and it forms shell on electrode active material 40
Protective layer (metal or metalloid, nitrogen or phosphor codoping clad).That is, carbonisation forms one altogether on electrode active material
Adulterate carbon-coating 44.In carbonisation, hydrogen, oxygen and carbon may be from double (double organic bags of organic layer clad electrode active material 43
Coating metal oxide or double organic coating layer metal phosphates) in water (H2) and carbon dioxide (CO O2) form decompose or
It is evaporated.Therefore, most metals atom or metalloid atom and nitrogen or phosphorus atoms will stay in clad as dopant
On 44A.
It will be noted that pass through compound (its formation pair for selecting to use in the reaction of the chemical graft of step 402 and 403
Organic coating layer electrode active material 43), it may be determined that the concentration of dopant.For example, gold in the organo-metallic compound of selection
Category or metalloid (being used for the graft reaction of step 402, to be reacted with protonation electrode active material 41) content are higher,
Metal or metalloid in the organic coating layer of doped carbon (layer 44A) after double organic coating layer electrode active materials 43 and carbonization
Concentration it is higher, vice versa.Similarly, in the graft reaction of step 403 with organic coating layer electrode active material 42
Nitrogen content is higher in the compound reacted and used, the doping after double organic coating layer electrode active materials 43 and carbonization
The concentration of nitrogen is higher in the organic coating layer of carbon (layer 44A), and vice versa.Equally, with having in the graft reaction of step 403
Phosphorus content is higher in the compound that machine clad electrode active material 42 is reacted and used, in double organic coating layer electrode actives
Property material 43 and carbonization after doped carbon (layer 44A) organic coating layer in phosphorus concentration it is higher, vice versa.
As indicated by a step 404, electrode material 44 includes electrode active material 40 and codope carbon-coating 44A.Layer 44A be mainly
Carbon, also metalic contamination or metalloid ooze debris and N doping thing or phosphorous dopants.In other words, layer 44A main component
It is carbon.Metalloid or metal and nitrogen or phosphorus can be micro.Metalloid or metal and nitrogen-atoms or phosphorus atoms are layer 44A's
Carbon atom is replaced on some positions.In the embodiment of the present invention, on layer 44A the atomic concentration of metal or metalloid be 5% or
Less.In the embodiment of the present invention, nitrogen atom concentration is 5% or less on layer 44A.In the embodiment of the present invention, rich in phosphorus
The compound of carbon is included in the reaction of step 403, and the phosphorus atom concentration on layer 44A is 5% or less.
In the carbonisation shown in step 404, hydrogen atom, oxygen atom and some carbon atoms can be decomposed.Due to for
The temperature of progress carbonisation is very high, and organic polymer material is dehydrated or decomposed.Hydrogen atom and oxygen atom pass through dehydration
And the water formed is evaporated into vapor from organic coating layer.Some carbon atoms are also decomposited from organic material to form titanium dioxide
Carbon.Because most of organic material is rich in carbon, after carbonisation, most of carbon is left on the surface of electrode active material 40
On.
Fig. 5 shows the clad electrode material 50 (identical with electrode material 44) of the embodiment of the present invention.Clad electrode material
Material 50 is formed by process 30, as described in above step 401-404.Electrode active material 500 is (with the phase of electrode active material 40
With) coated (identical with layer 44A) by shell protective layer 501.Electrode active material 500 can include reactive metal oxides or gold
Belong to phosphate material such as LiCoO2、LiNiO2、LiMn2O4、LiFePO4、LiNiO2、LiNi1/3Mn1/3Co1/3O2、
LiNi0.5Mn0.3Co0.2O2、xLi2MO3·(1-x)LiMeO2(0<x<1, M and Me be it is independent, it is at least one be from manganese, nickel,
Cobalt), Fe3O4、SnO2And combinations thereof.Due to the chemical reaction described in step 401-404, shell protective layer 501 is chemically bound
Onto electrode active material 500.For a specific lithium ion battery, electrode active material 500, material clad can be with
It is that negative material or positive electrode or both have concurrently.Shell protective layer 501 can include a composite construction, and it includes (1) gold
Category or metalloid and (2) nitrogen or phosphorus, the co-dopant as carbon.
Shell protective layer 501 solves following two big challenges simultaneously：(1) guard electrode active material 500 is from lithium ion
The harm of the corrosive byproducts formed in battery unit such as hydrogen fluoride；And (2) have the protection of defencive function except providing
Outside material, and there is higher electric conductivity.In other words, in the embodiment of the present invention, shell protective layer 501 has dual work(
Energy.Defencive function refers to that protective layer 501 serves as the scavenger of Corrosive Materia such as hydrogen fluoride, so as to guard electrode activity material
Material 500 is from corroding.So, shell protective layer 501 relieves the threat of unwelcome HF accessory substances.
In an embodiment of the present invention, the metalic contamination of shell protective layer 501 or metalloid dopant surround live electrode
Active material 500, on the surface of electrode active material 500.Another function of shell protective layer 501 is shell protection
N doping thing (or phosphorous dopants) in layer 501 can improve the electric conductivity (with pure carbon phase ratio) of shell protective layer 501, thus improve
The electric conductivity of electrode made of clad electrode material 50, monolithic conductive is improved (with other electricity made of carbon coating layer
Compare pole).Because when carbon material (valence state+4) is doped with atom (such as the nitrogen-atoms or phosphorus of valence state+5 of higher valence state
Atom) when, one or more electronics from dopant (nitrogen-atoms or phosphorus atoms) be able to will move freely, so as to improve
Electric conductivity.The electric transmission that the raising of electrode conductivuty will be helpful to during charge/discharge.
According to an embodiment of the invention, protective layer 501 provides the stability of fabulous clad.Electrode active material
Chemical bonding between 500 (such as metal oxide electrode materials) and protective layer 501 helps to realize that this excellent clad is steady
It is qualitative.In addition, chemical bonding also improves the conduction between electrode active material 500 and shell protective layer 501.
In addition, protective layer 501 is still uniform.In other words, the thickness of the protective layer 501 generated according to embodiments of the present invention
Change is very little.For example, when thickness change is less than or equal to 20%, the layer is substantially uniform.Those skilled in the art
Think, reacted with the chemical graft of organic metal additive and cause protective layer 501 with nitrogen and the reaction of the chemical graft of carbon source
Thickness is uniform.
According to an embodiment of the invention, due to nonmetalloid (such as nitrogen, phosphorus) dopant of+5 valencys, pair of protective layer 501
Function clad improves electric transmission, and provides material simultaneously and reacted with harmfulness or corrosive byproducts, prevents
Material decomposites from electrode active material 500 to be come.Although the valency of use of the embodiment of the present invention+5 is nonmetallic, can also make
Other by the use of other valence states nonmetallic are used as+5 valency nonmetal doping agent substitutes.Therefore, the embodiment of the present invention can include：In advance
The nonmetallic of suitable specific valence state (such as+5 or higher valence state) is first determined, and is based at least partially on this and predefines,
Select nonmetallic to be used as dopant.
The embodiment of the present invention can include a type of dopant, as metal dopant, metalloid doping, N doping or
Phosphorus dopant.The embodiment of the present invention can also include the combination of different types of following dopant：Metal dopant, metalloid are mixed
Miscellaneous dose, nitrogen dopant, phosphorus dopant, other appropriate dopants and combinations thereof.Therefore, according to the implementation of the present invention
Example, " doping " includes the dopant of one or more types, such as single doping-mono- dopant；- two kinds of dopants of codope, three
- three kinds of dopants of doping etc..
View 52 is the decomposition view of protective layer 501.View 52 show protective layer 501 include metallic atom M' located immediately at
The surface of electrode active material 500.That is metallic atom M' is in 501 innermost part of protective layer.View 52 also shows that nitrogen is mixed
The miscellaneous dose of outer layer for being located at protective layer 501.The relevant position of each dopant atom is that such as step 402 and 403 chemistry shown connect
The result of branch reaction order of occurrence.In an embodiment of the present invention, lithium ion battery (such as lithium ion battery 60) is coated with
The electrode of the electrode active material 500 of protective layer 501.Electrode (such as positive pole 601) can as it is a kind of include 94% containing coating
Li1.2Mn0.6Ni0.2O2(lithium-rich anode material, LRCM), 3% acetylene carbon black and 3% Kynoar (PVDF) are dissolved in N- first
The slurry of base pyrrolidones (NMP) is made.In an embodiment of the present invention, slurry is uniformly coated on aluminium by a kind of coating device
On paper tinsel (current collector), and it is dried in vacuo 12 hours by 120 DEG C, so as to form electrode.Lithium ion battery 60 is included by containing coating
Electrode material 50 made of positive pole 601, electrolyte 602, diaphragm 603 and negative pole 600.Positive pole 601 includes electrode active material
500, it is chemically bonded to protective layer 501, as described above.It should be pointed out that in an embodiment of the present invention, any electrode or two
Electrode can include clad as described above and guard electrode active material.That is, either in positive pole (such as negative pole
601), negative pole (such as negative pole 600), or both, can be all made up of the electrode material 50 containing coating.
Fig. 7 A and 7B show according to embodiments of the present invention it is coated before and after electrode material (lithium-rich anode material
(LRCM)Li1.2Mn0.6Ni0.2O2).Fig. 7 A are shown in the electrode active material before coated metalloid (silicon) nitrogen co-doped carbon.Figure
7B is shown in the electrode active material after coated metalloid (silicon) nitrogen co-doped carbon.Transmitted electron before and after coated shows
The comparison of micro mirror (TEM) image shows the contrast between electrode active material and coating.In figure 7b, it is relatively bright
Region is coating, and this is the shell composite of codope carbon (doped carbon has silicon atom (metalloid atom) and nitrogen-atoms).
It should be pointed out that the coating is very uniform, there is about 3nm thickness.
Fig. 8 A and 8B show the X ray light of the electrode for being coated with silicon (metalloid)-nitrogen co-doped carbon of the embodiment of the present invention
Electron spectrum (XPS).Fig. 8 A show it is coated before (solid dot) and (hollow dots) afterwards it is high-resolution
Li1.2Mn0.6Ni0.2O2The Si2p XPS spectrums of (rich lithium titanate cathode material, LRCM).Fig. 8 B show it is coated before (solid dot) and it
The high-resolution Li of (hollow dots) afterwards1.2Mn0.6Ni0.2O2The N1s XPS spectrums of (lithium-rich anode material, LRCM).X ray light
Electron spectrum (XPS) is the knot for being used to determine the element (such as silicon and nitrogen) in metal/metalloid-nitrogen co-doped carbon coating electrode
Close energy.For the lithium-rich anode material containing coating, the formation of Si-C keys in coating is can be shown that in 102eV combination.
400eV combination can confirm that the presence of N-C keys in coating lithium-rich anode material.According to these results, it can be deduced that conclusion：
In metalloid-nitrogen co-doped carbon, silicon is bonded with carbon geochemistry, and nitrogen is bonded with carbon geochemistry.Do not examined in original lithium-rich anode material
Measure such as Si-C and N-C chemical bonding.It was therefore concluded that metalloid and nitrogen are co-doped with by chemical bonding
It is miscellaneous in carbon containing clad.
Fig. 9 show the embodiment of the present invention lithium-rich anode material surface clad/metalloid-nitrogen co-doped carbon before and
Chemical impedance spectrogram afterwards.According to an embodiment of the invention, before and after metal/metalloid-nitrogen co-doped carbon is coated
Carry out electrochemical impedance spectroscopy analysis.As illustrated, before cladding, the internal resistance of button cell, about 250 ohm, cladding
Afterwards, about 50 ohm.Therefore, the effect of metal/metalloid-nitrogen co-doped carbon coating is that the electric conductivity of electrode material is
Improve.In one embodiment, (lithium-rich anode material, Li1.2Mn0.6Ni0.2O2) on be coated with silicon and nitrogen co-doped carbon-coating,
The resistance variations R of the nitrogen co-doped carbon of metalloid1/R0It is 0.25, wherein R1Be cladding after electrode internal resistance, R0Before being cladding
Electrode internal resistance.R1/R0It is worth smaller, shows that the improvement of the internal resistance of covering material is better.
In addition, the method for the embodiment of the present invention or the product prepared by this method include any of following characteristics (a) to (x)
Combination.This method can be used for the cladding of the electrode active material of lithium ion battery.
(a) chemical bonding doped carbon is carried out to electrode active material.
(b) doped carbon can at least doped with:(1) a kind of metal or metalloid and (2) one nonmetallic, its valence state is different from
The valence state of carbon (such as+5 or bigger valence states).
(c) chemical bonding can include：Chemical bond unifies organic layer to electrode active material；And organic layer is converted into
Doped carbon.
(d) chemical bond unification organic layer can include：The surface of electrode active material is protonated, to produce hydroxyl (- OH)
Functional group is on the surface.
(e) an organic metal additive is used, metallic atom or metalloid atom are attached to matter in a manner of chemical graft
On sonization surface and form first layer.
(f) carbon and non-metal source are added to the first layer in a manner of chemical graft, to form the second of the organic layer
Layer.
(g) protonation can be by electrode active material metal oxide or metal phosphate and an organic solvent containing acid
Reacted.
(h) reaction of metal oxide or metal phosphate and acid includes：Hydrogen Proton is chemically bonded to metal oxide
Or on metal phosphate.
(i) metal oxide or metal phosphate can be selected from：LiCoO2、LiNiO2、LiMn2O4、LiFePO4、LiNi1/ 3Mn1/3Co1/3O2、LiNi0.5Mn0.3Co0.2O2、xLi2MO3·(1-x)LiMeO2(0<x<1, M and Me be it is independent, it is at least one come
From manganese, nickel, cobalt), Fe3O4、SnO2, and combinations thereof.
(j) acid can be selected from：Acetic acid, oxalic acid, formic acid, citric acid, and combinations thereof.
(k) organic solvent can be selected from：Methanol, ethanol, isopropanol and acetone.
(l) metallic atom or metalloid atom are added in first layer in a manner of chemical graft and can included：Organic metal
Additive is reacted with protonation surface.
(m) organic metal additive can be selected from：Siliceous, aluminium, titanium, the coupling agent of zirconium and combinations thereof.
(n) coupling agent of organic metal additive can include following functional group such as epoxy radicals, alkoxy and amine including different
(ethylenediamine base-N- ethyoxyls) titanate esters of propoxyl group three and 3- glycydoxies trimethoxy silane and they
Combination.
(o) metallic atom or metalloid atom can be selected from：Titanium, aluminium, silicon, tin, magnesium, zinc, zirconium and combinations thereof.
(p) the most the inside of first layer can include the metallic atom or metalloid atom.
(q) nitrogen and carbon source can be selected from：Melamine, polyethyleneimine, polyacrylamide, pyrroles and its combination.
(r) outermost of the second layer can include nitrogen and carbon source, or phosphorus and carbon source.
(s) organic layer can be heat-treated in carbonisation.
(t) heat treatment is that organic layer is heated to 400-1200 DEG C of temperature under following atmosphere：Argon gas, helium, nitrogen,
Hydrogen, carbon dioxide or combinations thereof.
(u) carbon can be by a variety of different types of atom doped.
(v) carbon can be carbon co-doped.
(w) codope carbon can include (1) nitrogen or phosphorus, and (2) metal or metalloid, as dopant.
(x) doping carbon-coating includes auto-dope carbon.
In addition, the device or system of the embodiment of the present invention include any combination in following characteristics (1) to (11).The device
Or system can be lithium ion battery, the electrode of lithium ion battery or the material for manufacturing lithium ion cell electrode.
(1) device or system include electrode active material, have doped carbon to be chemically bonded on the electrode active material,
Wherein the doped carbon is at least nonmetallic doped with a kind of (1) metal or metalloid and (2) one, and its valence state is different from the valence state of carbon
(such as valence state+5 or bigger valence state).
(2) electrode active material can be selected from：Metal oxide, metal sulfide, metal phosphate and their group
Close.
(3) innermost layer of doped carbon can include metallic atom or metalloid atom.
(4) metallic atom or metalloid atom can be selected from：Titanium, aluminium, silicon, tin, magnesium, zinc, zirconium.
(5) outermost layer of doped carbon can include the nonmetallic of+5 valencys.
The nonmetallic of (6)+5 valencys can include nitrogen or phosphorus.
(7) concentration of nitrogen or phosphorus can be equal to or less than 5% in doped carbon.
(8) concentration of the metal in doped carbon or metalloid is equal to or less than 5%.
(9) doped carbon is the clad that a layer thickness is 2-50 nanometers.
(10) it is uniform one layer to adulterate carbon-coating, if the thickness of this layer changes, that described change is less than or equal to
20%.
(11) doping carbon-coating includes auto-dope carbon.
The embodiment of the present invention provides a kind of method for coating, and metal oxide and three-dimensional porous carbon base body are coated into lithium ion
On the electrode material of battery.Generally, the cladding Rotating fields are that metal oxide is embedded into porous carbon base body, as Figure 10 is shown.
The percentage by weight of carbon and metal oxide is 1~10% and 0.1~1% in final products.The thickness of clad 20~
In the range of 200nm.Further, since using pore creating material (such as surfactant), loose structure can also be produced in clad.Bag
Aperture in coating is 2~50nm.
The embodiment of the present invention utilizes coupling agent (such as titanate coupling agents), by the electrode material surface in a solvent that suspends
Functionalization, polymerisation then is carried out using appropriate polymer, to produce polymer overmold on electrode material.Coupling agent and
Chemical bonding between electrode active material so that the clad on electrode material is evenly.In order to produce porous carbon coating
Layer, pore creating material (such as surfactant) is added in the course of the polymerization process, this is carried out at 80 DEG C, in order to which solvent evaporates.So
The polymer of jacketed electrode material is dried afterwards, is then carbonized in an inert atmosphere at a temperature of about 1000 DEG C.Coupling agent,
Polymer and surfactant are the sources of carbon material and metal oxide (such as titanium dioxide) particle.Gold in carbon coating layer
Category oxide plays hydrogen fluoride (hydrogen fluoride is that performance of lithium ion battery can be made to produce decline in charge/discharge process) scavenger
Effect.Above-mentioned preparation process comprises the following steps, and shows in Fig. 10.
(1) electrode material is surface-functionalized.Electrode material (such as silicon, lithium-rich anode material) is evenly dispersed in organic
In solvent (such as alcohol), wherein being used for comprising organic metal coupling agent (such as M=Al and Ti) surface-functionalized.In addition, in order to wrap
Loose structure is formed on coating, addition triblock copolymer is as soft template.
(2) polymerization of electrode surface.Addition has suitable functional group (such as-NH in above-mentioned solution2Or epoxide group)
Polymer, to generate polymer on electrode active material surface under suitable temperature (such as 80 DEG C).Polymerization process is to pass through
Heat coupling agent and polymer and realize.Polymer is long chain hydrocarbons, and with the functional group that polymerisation occurs with coupling agent.
(3) it is carbonized in an inert atmosphere.The polymer formed on electrode active material will be built up to be dried, with laggard
Row carbonization.Can be at a temperature of 1000 DEG C and in inert atmosphere (such as N2) in carbonization composite, by metal oxide and
Carbon base body is coated on electrode active material.
In above-mentioned steps (1), organic metal coupling agent can be silane or zirconium coupling agent.For suspension electrode activity material
The organic solvent of material can be methanol, ethanol, acetone or toluene.In above-mentioned steps (2), the temperature of polymerisation can 60~
In the range of 200 DEG C.In above-mentioned steps (3), carburizing temperature can be 400~2000 DEG C, and inert atmosphere can be argon gas, helium
Gas or their mixture.
The ordinary clads of electrode active material are typically due to electrode material and coat the physical mixed (such as ball-milling method) in source,
So it is the uneven clad of uncontrollable thickness.According to the present invention, coating thickness and composition can be by changing shell
The ratio of middle metal oxide and carbon content controls.The strong chemical bond being additionally, since between coupling agent and electrode active material
Close, uniform clad can be produced.Therefore, it can realize that there is controllable coating thickness and composition in electrode material surface
Uniform clad.The clad technology is expected to improve electric conductivity, and provides protection for the electrode active material of lithium ion battery.
Although the present invention and its superiority is described in detail, it should be appreciated that do not departing from appended claims definition
The present invention under conditions of can make various changes, replacement and change.In addition, scope of the present application be not limited to it is described herein as
The specific embodiment of processing procedure, machine, manufacture, material composition, means, method and steps described in book etc..This area
Ordinary skill as can be easily understood from the description, can be utilized according to the present invention and substantially performed and phase described herein
Answer embodiment identical function or realize the current existing of identical result or the processing procedure developed in the future, machine,
Manufacture, material composition, means, method and steps.Therefore, appended claims are intended to include these processing procedures, machine, system
Make, material composition, means, method or step.
Claims (49)
1. a kind of method for coating of the electrode active material of lithium ion battery, including step：
Doped carbon is coated on the electrode active material in a manner of being chemically bonded, the doped carbon is at least doped with (1)
A kind of metal or metalloid, and (2) are a kind of nonmetallic, and its valent state is different from the valent state of the carbon, the chemical bond
The step of conjunction, includes：
One organic layer is chemically bonded on the electrode active material；And the organic layer is changed into the doped carbon;
The step of organic layer wherein is chemically bonded into the electrode active material includes：
The surface of the electrode active material is subjected to protonation processing, to produce hydroxyl (- OH) functional group on said surface；
Organic matter containing metallic atom or metalloid atom is added to the protonation surface in a manner of chemical graft, to produce
First layer；
The organic matter of carbon containing and described non-metal source is added to the first layer in a manner of chemical graft, to form the organic layer
The second layer.
2. the method as described in claim 1, wherein the Protonation Step includes：
Metal oxide in the electrode active material or metal phosphate are reacted with an organic solvent containing acid.
3. method as claimed in claim 2, wherein by the metal oxide or metal phosphate and the having containing acid
The step of solvent is reacted includes：Hydrogen Proton is chemically bonded on the metal oxide or the metal phosphate.
4. method as claimed in claim 2, wherein the metal oxide or metal phosphate are selected from：LiCoO2、LiNiO2、
LiMn2O4、LiFePO4、LiNi1/3Mn1/3Co1/3O2、LiNi0.5Mn0.3Co0.2O2、xLi2MO3• (1-x)LiMeO2、Fe3O4And
SnO2, and combinations thereof, wherein 0<x<1, M and Me is independent, and at least one from manganese, nickel, cobalt.
5. method as claimed in claim 2, wherein the acid is selected from：Acetic acid, oxalic acid, formic acid, citric acid, and combinations thereof.
6. method as claimed in claim 2, wherein the organic solvent is selected from：Methanol, ethanol, isopropanol and acetone.
7. the method as described in claim 1, wherein by the organic matter containing metallic atom or metalloid atom with chemical graft
Mode be added to it is described protonation surface to produce first layer the step of include：By an organic metal additive or coupling comprising silicon
Agent is reacted with the protonation surface.
8. method as claimed in claim 7, wherein the organic metal additive is selected from：Comprising aluminium, titanium, zirconium, and combinations thereof
Coupling agent.
9. method as claimed in claim 7, wherein the coupling agent of the organic metal additive includes the (second two of isopropoxy three
Amido-N- ethyoxyls) titanate esters, the coupling agent comprising silicon includes 3- glycydoxy trimethoxy silanes.
10. method as claimed in claim 7, wherein the metallic atom or metalloid atom be selected from titanium, aluminium, silicon, tin, magnesium,
Zinc, zirconium, and combinations thereof.
11. the method as described in claim 1, wherein the most the inside of the first layer includes the metallic atom or the eka-gold
Belong to atom.
12. the method as described in claim 1, wherein the organic matter of the doped carbon and non-metal source is selected from：Melamine, gather
Aziridine, polyacrylamide, pyrroles, and combinations thereof.
13. the method as described in claim 1, wherein the outermost of the second layer includes the doped carbon and non-metal source.
14. the method as described in claim 1, wherein the step of organic layer is changed into doped carbon includes：It had been carbonized
The organic layer is heat-treated in journey.
15. method as claimed in claim 14, wherein the heat treatment step includes：By the organic layer in following atmosphere
The temperature being heated in the range of 400-1200 °C：Argon gas, helium, nitrogen, hydrogen, and combinations thereof.
16. the method as described in claim 1, wherein the doped carbon is codope carbon.
17. method as claimed in claim 16, wherein the codope carbon includes nitrogen or phosphorus, and metal or metalloid, as
Dopant.
18. the method as described in claim 1, wherein the doped carbon includes auto-dope carbon.
19. a kind of lithium ion battery, including an electrode, the electrode include：Electrode active material with doped carbon, it is described to mix
Miscellaneous carbon is coated in a manner of being chemically bonded on the electrode active material, wherein the doped carbon at least doped with（1）It is a kind of
Metal or metalloid and（2）It is a kind of nonmetallic, wherein the nonmetallic valent state is different from the valent state of carbon.
20. battery as claimed in claim 19, wherein the electrode active material is selected from：Metal oxide, metal sulfide,
Metal phosphate, and combinations thereof.
21. battery as claimed in claim 19, wherein the innermost layer of the doped carbon includes the metal or the metalloid.
22. battery as claimed in claim 19, wherein the metal or the metalloid are selected from：Titanium, aluminium, silicon, tin, magnesium, zinc,
And zirconium.
23. battery as claimed in claim 19, wherein the outermost layer of the doped carbon is including described nonmetallic, it is described nonmetallic
Valent state be+5.
24. battery as claimed in claim 23, wherein the valent state+5 is nonmetallic including nitrogen or phosphorus.
25. battery as claimed in claim 24, wherein the atomic concentration of the nitrogen or phosphorus in the doped carbon is equal to or small
In 5%.
26. battery as claimed in claim 19, wherein the atomic concentration of the metal or metalloid in the doped carbon etc.
In or less than 5%.
27. battery as claimed in claim 19, wherein the thickness degree of the doped carbon is 2-50 nm.
28. battery as claimed in claim 19, wherein the thickness degree of the doped carbon is uniform, it is described uniformly refer to it is described
The change of thickness is less than or equal to 20%.
29. battery as claimed in claim 19, wherein the doped carbon includes auto-dope carbon.
30. a kind of material for being used to make lithium ion cell electrode, the material include：Electrode activity material with doped carbon
Material, the doped carbon is coated in a manner of being chemically bonded on the electrode active material, wherein the doped carbon is at least adulterated
Have（1）A kind of metal or metalloid and（2）It is a kind of nonmetallic, wherein the nonmetallic valent state is different from the chemical valence of carbon
State.
31. material as claimed in claim 30, wherein the electrode active material is selected from：Metal oxide, metal sulfide,
Metal phosphate, and combinations thereof.
32. material as claimed in claim 30, wherein the innermost layer of the doped carbon includes the metal or the metalloid.
33. material as claimed in claim 30, wherein the metal or the metalloid are selected from：Titanium, aluminium, silicon, tin, magnesium, zinc,
And zirconium.
34. material as claimed in claim 30, wherein the outermost layer of the doped carbon is including described nonmetallic, it is described nonmetallic
Valent state be+5.
35. material as claimed in claim 34, wherein the valent state+5 is nonmetallic including nitrogen or phosphorus.
36. material as claimed in claim 35, wherein the atomic concentration of the nitrogen or phosphorus in the doped carbon is equal to or small
In 5%.
37. material as claimed in claim 30, wherein the atomic concentration of the metal or metalloid in the doped carbon etc.
In or less than 5%.
38. material as claimed in claim 30, wherein the thickness degree of the doped carbon is 2-50 nm.
39. material as claimed in claim 30, wherein the thickness degree of the doped carbon is uniform, it is described uniformly refer to it is described
The change of thickness is less than or equal to 20%.
40. material as claimed in claim 30, wherein the doped carbon includes auto-dope carbon.
41. a kind of product for being used to make lithium ion cell electrode, manufacturing process include：
Doped carbon is chemically bonded on electrode active material, wherein the doped carbon at least doped with（1）A kind of metal or class
Metal and（2）It is a kind of nonmetallic, wherein the nonmetallic valent state is different from the valent state of carbon；Wherein described chemical bond
Conjunction includes：
One organic layer is chemically bonded on the electrode active material；
The organic layer is changed into the doped carbon；
A step of organic layer wherein is chemically bonded into the electrode active material includes：
By the surface protonated processing of the electrode active material, to produce hydroxyl (- OH) functional group on said surface；
Organic matter containing metallic atom or metalloid atom is added to the protonation surface in a manner of chemical graft, to produce
First layer；
The organic matter of carbon containing and described non-metal source is added to the first layer in a manner of chemical graft, to form the organic layer
The second layer.
42. product as claimed in claim 41, wherein the step of protonation includes：
The metal oxide of the electrode active material or metal phosphate are reacted with an organic solvent containing acid.
43. product as claimed in claim 42, wherein by the metal oxide or metal phosphate with containing the organic of acid
The step of solvent is reacted includes：Hydrogen Proton is chemically bonded on the metal oxide or the metal phosphate.
44. product as claimed in claim 41, wherein the organic matter containing metallic atom or metalloid atom is connect with chemistry
Branch mode be added to it is described protonation surface to produce first layer the step of include：By an organic metal additive and the protonation
Reacted on surface.
45. product as claimed in claim 41, wherein the most the inside of the first layer includes the metallic atom or the class
Metallic atom.
46. product as claimed in claim 41, wherein the outermost of the second layer includes the doped carbon and non-metal source.
47. product as claimed in claim 41, wherein the step of organic layer is changed into doped carbon includes：It had been carbonized
Cheng Zhong, the organic layer is heat-treated, the organic layer is heated to 400-1200 °C of temperature in following atmosphere：Argon
Gas, helium, nitrogen, hydrogen, and combinations thereof.
48. product as claimed in claim 41, wherein the doped carbon at least auto-dope has（1）Nitrogen or phosphorus, and（2）Metal or
Metalloid.
49. product as claimed in claim 41, wherein the product includes Li1.2Mn0.6Ni0.2O2Nano particle, and be coated with
The doped carbon.
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| US14/796,816 US20160036049A1 (en) | 2014-07-30 | 2015-07-10 | Lithium ion battery electrode material with composite functional coating |
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| CN106784677A (en) * | 2016-12-16 | 2017-05-31 | 江南大学 | A kind of preparation of lithium-enriched cathodic material of lithium ion battery and improved method |
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