CN105006547A - Lithium-ion battery and coating method of electrode active material of lithium-ion battery - Google Patents
Lithium-ion battery and coating method of electrode active material of lithium-ion battery Download PDFInfo
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- CN105006547A CN105006547A CN201510460476.8A CN201510460476A CN105006547A CN 105006547 A CN105006547 A CN 105006547A CN 201510460476 A CN201510460476 A CN 201510460476A CN 105006547 A CN105006547 A CN 105006547A
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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 lithium-ion battery and a coating method of an electrode active material of the lithium-ion battery, and relates to chemical grafting of an organic layer to the surface of an electrode material. The method comprises: carbonizing the organic layer to form a doped carbon layer on the surface of the electrode material in a chemical bonding manner; and reacting a doped substance in the doped carbon layer with a hazardous substance formed in a charging and discharging process of the lithium-ion battery to protect the electrode material, wherein the doped substance in the doped carbon layer can improve the electrical conductivity of the doped carbon layer. The invention further provides the lithium-ion battery, the electrode material of which comprises the carbon layer doped in a chemical bonding layer. The doped substance can react with the hazardous substance resulting from electrolyte decomposition in the charging and discharging process of the lithium-ion battery. The doped substance contained in the doped carbon layer can improve the transmission rate of electrons, so that the electrical conductivity of the electrode material and an electrode prepared from the electrode material is improved.
Description
[related application]
This application claims the priority of U.S. Provisional Application 62/030936, this U.S. Provisional Application is being entitled as " METHOD OF MAKING POROUSCOATING ON ELECTRODE MATERIALS FOR LITHIUM IONBATTERIES " of submission on July 30th, 2014, and its disclosure is incorporated into the application by reference.
[technical field]
The present invention relates to field of batteries, particularly by providing novel coating layer and coating technology to improve performance of lithium ion battery with guard electrode material and the electrode conductivuty increasing lithium ion battery.
[background technology]
Many modern comforts all need battery as mobile electric energy.Because the packaged type energy, need the equipment of electric energy such as computer, flashlight, wrist-watch and miscellaneous equipment just can be of portable form.Even when battery is not the main energy sources of an equipment, but this equipment still can need battery.Such as, most of automobile provides major impetus by burns gasoline, but these automobiles still need a battery, to make the engine start of automobile.Because to the concern of environment, automobile also uses battery to replace gasoline as main power source now gradually.Therefore, battery and battery technology become more and more general and important.
There is various types of rechargeable battery on the market.The basic conception of rechargeable battery is exactly the electrochemical cell that chemical energy is reversibly converted to electric energy by them.Each battery unit has a positive terminal (positive pole), and electronics through an external circuit, flows to a negative pole end (negative pole) from this positive terminal.Electronics displacement generation current.Electric current can be provided for the device be connected between positive pole and negative pole.
Because lithium ion battery has certain advantage than other types rechargeable battery, they are more and more welcome, are widely used in the equipment such as such as mobile phone, computer and electric automobile.Fig. 1 shows lithium ion battery 10 and the operation principle thereof of prior art.The primary clustering of lithium ion battery 10 comprises negative pole 100, positive pole 101, electrolyte 102 and barrier film 103.
Barrier film 103 as separating negative pole 100 and positive pole 101, thus prevents the short circuit between negative pole 100 and positive pole 101.Positive pole 101 is cobalt acid lithium normally; Negative pole 100 is graphite or tin-based material normally.In lithium ion battery 10 charging process, lithium ion can be discharged into electrolyte 102 from positive pole 101, then moves to negative pole 100, the right namely from the left side of Fig. 1 to Fig. 1.Electronics also spontaneously moves to negative pole 100 from positive pole 101 by an external circuit.In discharge process, move to positive pole 101 at the lithium ion of negative pole 100 and electrons from negative pole 100, namely on the right of Fig. 1 to the left side of Fig. 1.For the charging and discharging process of lithium ion battery, the movement between negative pole and positive pole of lithium ion and electronics is very important.
In the art, it is desirable to produce the lithium ion battery with high-energy-density.In view of pursuing high-energy-density, electrode material (negative material and positive electrode) has become an important focus areas, because they have appreciable impact to the energy density improving lithium ion battery.Except energy density, electrode material also determines the capacity of lithium ion battery to a considerable extent.
Table 1 shows as some typical materials of negative active core-shell material and positive electrode active materials and their respective conductances thereof.As can be seen from Table 1, compare with material with carbon element, the conductance being used in some typical negative electrode materials in lithium ion battery and advanced positive electrode material is quite low.
Table 1
| Active material | Negative pole/positive pole | Conductance (S/cm) |
| Cobalt acid lithium LiCoO 2 | Negative pole | 2.0×10 -1 |
| LiFePO4 LiFePO 4 | Negative pole | 1.9×10 -9 |
| Silicon dioxide SiO 2 | Positive pole | 1.0×10 -11 |
| Tin ash SnO 2 | Positive pole | 1.0×10 -3 |
| Carbon Carbon | N/A | 1.0×10 4 |
As can be seen from Table 1, the chemical formula of positive electrode shows, lithium (Li) is one of key element of positive electrode.Table 1 also shows, and negative material can be metal oxide.
In lithium ion battery 10 running, when working at more than high voltage 4.8V, electrolyte 102 decomposes according to following chemical equation, LiPF wherein
6be the major solute of electrolyte, be widely used in lithium ion battery:
LiPF
6+H
2O→LiF+POF
3+2HF (1)
Decomposition reaction occurs in charge/discharge process, can form hydrogen fluoride (HF).Conversely, hydrogen fluoride can corrode (reacting with it) cobalt acid cathode of lithium 101:
4HF+LiCoO
2→LiF+CoF
3+2H
2O (2)
Chemical equation (2) display cobalt element forms cobalt trifluoride (CoF from positive pole stripping
3).Cobalt trifluoride is in the electrolytic solution.Cobalt is from positive pole stripping and be discharged into electrolyte, is disintegrated by positive electrode, and causes battery performance to worsen.
The Surface coating of electrode material is the effective ways solving electrode material dissolves (namely harmful in charge/discharge process accessory substance).In the prior art, coated shortcoming comprises complicated preparation technology, one pack system is coated and non-homogeneous coated.The method for coating of many maturations comprises sol-gel process, ball-milling method, wet-mix process, chemical vapour deposition (CVD), spray pyrolysis, electrostatic spinning and hydro thermal method, and they have higher preparation cost and higher energy ezpenditure.Current most of Surface coating is one-component layer, effectively can not avoid stripping by guard electrode material in charge/discharge process.
Such as, the surface coating layer attempting using carbon as electrode material has been had.But because carbon is inert component, it just can not avoid chemical stripping by guard electrode material effectively.Carbon can provide the temporary barrier between HF and electrode material at most.If carbon is porous, hydrogen fluoride in the solution finally directly can contact and erosion electrode material with electrode.The another kind of method solving lithium ion battery electrode material metal dissolving problem uses metal oxide as sacrifice agent, reacts with HF.But, coating layer uses metal oxide, will the resistivity of electrode material be significantly improved.
The method of current electrode-clad also has a problem to be that the coating layer of gained is normally uneven.Particularly when using physical method to prepare these coating layers as ball-milling method, spray pyrolysis, usually there will be the problem that coating thickness is uneven.In non-homogeneous coating layer, the part of relative thin is its weak spot, removes directly to contact active material because they can offer an opportunity and reacts with it to HF.
The quality of electrode material coating layer, structure and feature are extremely important to battery performance.Therefore, in battery manufacturing field, always expect the coating layer that can improve battery electrode.
[summary of the invention]
The present invention relates to device, the system and method for protection battery electrode material, provide a sacrifice agent for being corrosive of producing in battery charge and discharge process or harmfulness accessory substance reacts.Embodiments of the invention can be applied to the lithium ion battery with high energy density worked under high voltage condition.This sacrifice agent can be arranged in coating layer, and it not only can improve the conductivity of coating layer, and can obtain mode guard electrode active material by chemical bonding.
In an embodiment of the present invention, in the coating layer of protected component material (such as electrode), an alloy is provided, as sacrifice agent.Sacrifice agent can be metal or metalloid.Such as, in an embodiment, corrosive byproducts is hydrogen fluoride, and the metalic contamination in electrode material coating layer or metalloid alloy can consume hydrogen fluoride.By this way, hydrogen fluoride directly cannot contact with electrode material, thus prevents the metal dissolving of electrode material.In other words, the alloy in coating layer, as the protective agent of electrode material, prevents the corrosive byproducts produced in charge and discharge process to the corrosion function of electrode material.
The embodiment of the present invention relates to the electrode material coating layer of lithium ion battery, this material mainly carbon.Carbon can have metal or metalloid by codope, to provide a sacrifice agent.In addition, carbon can also be different from the nonmetalloid (nitrogen, phosphorus as+5 valencys) of the valent state (as be greater than the valent state of carbon or be greater than a predetermined threshold value) of carbon doped with its valent state.Its valent state that adulterates in carbon is different from the nonmetalloid of the valent state of carbon (nitrogen or phosphorus as+5 valencys), can improve the conductivity of carbon coating layer.Although coating layer material is carbon mainly, not pure carbon, so use carbon as coating layer by this way, complex function coating layer can be thought.According to the embodiment of the present invention, carbon coating layer also comprises other materials as dopant, as metal, metalloid, nitrogen, phosphorus or their combination.These dopants can from the organic compound with functional group.Organic compound is used for reaction to form autodoping coating layer, it can guard electrode material from the erosion of side reaction, and improve the conductivity of electrode active material.
Except the characteristic for coating layer material, the present invention also proposes a kind of this coating layer material to be carried out coated method, which utilizes the chemical bonding between coating layer material and electrode material.Therefore, the embodiment of the invention discloses by doping carbon is chemically bonded to electrode material surface and be coated on the method for battery electrode material.This can comprise: be chemically bonded on electrode material by an organic layer first, then this organic layer be converted into doping carbon-coating.The embodiment of the present invention comprises a battery, and its electrode material chemical bonding has doping carbon.
Aforementionedly summarise characteristic sum technical advantage of the present invention quite widely, following detailed description of the present invention can be understood better.Further feature of the present invention and advantage will be described subsequently, and it forms the theme of the claims in the present invention.Those skilled in the art it should be noted that, the concept of disclosure and specific embodiment can be utilized like a cork as a basis, are used for revising or design can perform other structure of the identical object of the present invention.Those skilled in the art also should be realized that, this equivalent constructions does not offset the spirit and scope of the invention of setting forth in accessory claim.Be counted as the novel features of characteristic of the present invention, about its tissue and How It Works, with other object together with advantage, can be understood better from the description below in conjunction with accompanying drawing.But should profoundly recognize, being only be used as to describe and illustrative purposes at this each accompanying drawing provided, is not be intended to as restriction definition of the present invention.
[accompanying drawing explanation]
In order to more completely understand the present invention, referring now to the following drawings, embodiments of the invention are described, wherein:
Fig. 1 shows lithium ion battery and the operation principle thereof 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 coating layer electrode material of the embodiment of the present invention.
Fig. 6 shows the lithium ion battery of the embodiment of the present invention.
Fig. 7 A and 7B show the embodiment of the present invention coated before and after the transmission electron microscope image of electrode material.
Fig. 8 A show coated before the high-resolution Li of (solid) and (hollow) afterwards
1.2mn
0.6ni
0.2o
2the x-ray photoelectron power spectrum (XPS) of the Si2p of (lithium-rich anode material, LRCM).
Fig. 8 B show coated before the high-resolution Li of (solid) and (hollow) afterwards
1.2mn
0.6ni
0.2o
2the x-ray photoelectron power spectrum (XPS) of the N1s of (lithium-rich anode material, LRCM).
Fig. 9 show the embodiment of the present invention coated before and after electrochemical impedance spectroscopy (EIS) curve chart of electrode material.
Figure 10 shows a process of the embodiment of the present invention.
Should be appreciated that accompanying drawing is not necessarily pro rata, the disclosed embodiments just show schematic diagram and partial view sometimes.In some cases, can be omitted some and do not affect understanding details of the present invention.It will of course be appreciated that the present invention is not limited to described specific embodiment.
[embodiment]
The lithium ion battery with high working voltage has superiority in this area.But the lithium ion battery worked with high voltage (as 4.8 volts or higher), its battery electrode active material can corrode.As mentioned above, lithium ion battery can cause the decomposition of electrolyte during discharge and recharge, can produce corrosive hydrogen fluoride.As mentioned above, hydrogen fluoride can cause damage to electrode active material.Such as, hydrogen fluoride can with cobalt acid lithium LiCoO
2react, and cobalt element is discharged into electrolyte from electrode material.
Seeking to solve in the process of this problem (as hydrogen fluoride and lithium ion battery electrode material react), inventor recognizes, prevent the material for electrode material coating layer that electrode and harmful side product (HF) react, one of them Consideration is whether this coating layer material has high conductivity.The overall conductivity of electrode that another consideration factor is electrode-clad layer material and manufactures with electrode material.In some cases, expect to manufacture the battery that its electrode has high conductivity (low-resistivity).
The embodiment of the present invention provides a kind of sacrifice agent or scavenger, is used for avoiding electrode material to react with the harmfulness formed in battery or corrosive accessory substance.Thus Corrosive Materia, as hydrogen fluoride, would not directly react with electrode material and cause electrode material to corrode.The embodiment of the present invention also provides the sacrifice agent around electrode material surface.Such as, a protective layer can be provided, make this protective layer that can barrier be together set between corrosion products and electrode material.This protective layer also can be configured such that sacrifice agent to be centered around around electrode material on the surface of electrode material or both have concurrently, to react with harmfulness or corrosive byproducts.Above-mentioned protective layer can also be used to increase conductivity, can not improve the overall resistivity of electrode material and electrode while making guard electrode material.In addition, protective layer can be coated on electrode material by chemical bonding mode.
Fig. 2 shows a process 20 of the embodiment of the present invention.Process 20 protects for lithium ion cell electrode provides and improve the conductivity of lithium ion cell electrode.Process 20 starts from step 200, utilizes manufacture method known in the art to provide the material of lithium ion battery.Step 200 can provide the material of battery component, as electrode (negative pole and positive pole), electrolyte and diaphragm (shown in the lithium ion battery 10 being similar to Fig. 1 element).In step 201, the electrode material provided has a kind of sacrifice agent, in the coating layer of electrode material, be used for reacting with the corrosive byproducts formed at lithium ion battery duration of work (corrosive byproducts as formed during charge/discharge process).Step 202 configuration packet clad material is to improve its conductivity.It should be noted that, step 201 and step 202 can occur simultaneously.In step 203, comprise the electrode-clad layer material of sacrifice agent, be used to manufacture one or more electrode.
Such as, electrode (as negative pole) can be comprise 94% containing coating layer Li by one
1.2mn
0.6ni
0.2o
2the slurry that (lithium-rich anode material, LRCM), 3% acetylene carbon black and 3% Kynoar (PVDF) are scattered in 1-METHYLPYRROLIDONE (NMP) solvent is made.This slurry evenly can be coated on aluminium foil (current collector) by a kind of coating device, and by vacuumize under 120 degree of conditions 12 hours, thus form electrode.Except the electrode material of coated formation described here, above-mentioned electrode material and other assembly, as electrolyte, diaphragm etc., can be assembled in lithium ion battery and a kind ofly be similar to the lithium ion battery shown in Fig. 1 to be formed.
Fig. 3 shows the process 30 of the embodiment of the present invention.Process 30 protects for lithium ion cell electrode provides and improve the conductivity of lithium ion cell electrode.Process 30 starts from step 300, utilizes preparation method known in the art to provide the active component of lithium ion cell electrode.The other materials of lithium ion battery equally also can be provided.This material can comprise electrolyte and diaphragm (being similar to the element shown in Fig. 1 lithium ion battery).Electrode active material can be inorganic, metal oxide (MO), metal phosphate, metal sulfide or its combination.Electrode active material can be that inorganic, metal oxide and metal phosphate are as LiCoO
2, LiNiO
2, LiMn
2o
4, LiFePO
4, and SnO
2.At Fig. 4, shown electrode active material 40 be shown as one spherical, but also can be any shape.In embodiments of the invention, electrode active material can be Li
1.2mn
0.6ni
0.2o
2(lithium-rich anode material) nano particle, the about 200nm of particle diameter.
Process 30 is reacted by chemical graft and carbonisation and provide a kind of doping carbon coating layer for lithium ion battery electrode material subsequently.Chemical graft reaction and carbonisation will be described in step 301-304.In step 301, electrode active material 40 reacts with a kind of solution containing additive, with protonated preliminary treatment electrode active material 40.According to the embodiment of the present invention, surface protonated reaction and display is in the step 401 of Fig. 4.Additive solution can be weakly acidic solution, as any one acetic acid, oxalic acid, formic acid and citric acid at any one organic solvent as in isopropyl alcohol, methyl alcohol, ethanol, isopropyl alcohol or acetone, or its combination.Surface protonated reaction produces one or more functional group on electrode active material 40.Thus the surface of electrode active material 40 is covered by hydroxyl.The Surface Oxygen of the hydrogen ion in acid and metal oxide or metal phosphate reacts, thus the surface that formation one is protonated.As shown in step 401, electrode active material 40 forms chemical bond, forms protonated electrode active material 41 (protonated metal oxide or protonated metal phosphate) with hydrogen ion effect.Electrode active material can comprise metal oxide, metal phosphate, metal sulfide, combine as the similar material of active material or its for lithium ion battery.Compared with the method for other jacketed electrode active material, being formed in this area of above-mentioned chemical bond has greater advantage, and this can in following description.
Step 302 is the reactions of a kind of chemical graft, and as described in step 402, wherein protonated electrode active material 41 (protonated metal oxide or protonated metal phosphate) and a kind of organic metal additive react.Thus metal/metalloid atom is introduced in the organic coating layer of electrode active material 40.Organic metal additive can have a reactive functionality R
1(as epoxide group), an alkoxy grp R-O-and metallic atom or metalloid atom (as titanium, aluminium, silicon, tin, magnesium, zinc, zirconium and composition thereof).Organic metal additive can comprise silane, aluminium, titanium, zirconium and composition thereof as coupling agent.Coupling agent can comprise functional group as epoxy radicals, alkoxyl and amine, comprises isopropoxy three (ethylenediamine base-N-ethyoxyl) titanate esters and 3-glycydoxy trimethoxy silane, and composition.
In the chemical graft reaction of step 402, the protonated surface of organic metal additive and protonated electrode active material 41 (protonated metal oxide or protonated metal phosphate) is reacted, to produce electrode active material 42 and an accessory substance R-OH of organic coating layer.Therefore, in step 402, protonated surface and organic metal additive react on electrode active material 40 (metal oxide or metal phosphate) surface upper formation first Coated with Organic Matter layer.Electrode active material 40 envelopes by this organic matter layer.Hydrogen and the R-O group on protonated surface react, and can form accessory substance R-OH.Organic coating layer electrode active material 42 surrounds electrode active material 40 (metal oxide or metal phosphate) by the organic layer of metallic atom or metalloid atom.Metallic atom or metalloid atom are chemically bonded on the outer surface of metal oxide or metal phosphate.
In step 303, have another chemical graft to react, it adds the second organic layer to (organic layer is added on the electrode active material 42 of organic coating layer) on electrode active material 40, as described in step 403.According to embodiments of the invention, in the reaction of this chemical graft, the electrode active material 42 of organic coating layer and an organic compound being rich in nitrogen carbon react, to form the electrode active material 43 (metal oxide of two-layer organic coating layer) of two-layer organic coating layer.In addition, according to the embodiment of the present invention, react at this chemical graft, electrode active material 42 and the organic compound generation chemical reaction being rich in phosphorus carbon of organic coating layer, to form the electrode active material 43 (metal phosphate of two-layer organic coating layer) of two-layer organic coating layer.In addition, according in the embodiment of the present invention, react at this chemical graft, electrode active material 42 and (1) of organic coating layer are rich in the organic compound organic compound of nitrogen carbon and (2) being rich in phosphorus carbon and are reacted, to form the electrode active material 43 (metal oxide of two-layer organic coating layer and the metal phosphate of two-layer organic coating layer) of two-layer organic coating layer.Step 403 shows R
2-X is as being rich in the organic compound of nitrogen carbon or being rich in the organic compound of phosphorus carbon.X is nitrogen (or phosphorus) doping and carbon.Except nitrogen and carbon, this compound also has function functional group R
2.
Due to R
1and R
2between chemical reaction, the compound R of introducing
2-X is grafted on organic coating layer metal oxide.Therefore, if R
1epoxy radicals, R
2can be amido, vice versa (if i.e. R
1amido, R
2can be epoxy radicals).R
2-X can be melamine.Electrode active material 40 (metal oxide or metal phosphate), through these two chemical graft steps, is wrapped by two-layer organic material.
In the embodiment of the present invention, step 303 introduces an organic compound being rich in phosphorus carbon to organic coating layer, as described in step 403.Nitrogen is autodoping agent, because nitrogen-atoms is the presoma of doping carbon coating layer-organic coating layer.That is, nitrogen-atoms has existed in compound, forms organic coating layer for reaction.Like this, from other sources of some organic layer or doping carbon coating layer, nitrogen-atoms need not be incorporated in doping carbon coating layer.From another source, nitrogen is incorporated in carbon coating layer, comprises and use ammonia to obtain a coating layer material containing N doping.Therefore, in coating layer material, according to embodiments of the invention, nitrogen is the autodoping agent from nitrogen-enriched compounds.Nitrogen may be derived from the melamine for reacting with organic coating layer electrode active material 42.Nitrogen and carbon source may be from: melamine, polyethylene Asia amine, polyacrylamide, pyrroles and combination thereof.
In embodiments of the invention, the compound being rich in phosphorus carbon is included in the reaction of step 403.Phosphorus is autodoping agent, because phosphorus atoms is the presoma of doping carbon coating layer-organic coating layer.Namely phosphorus atoms has existed in compound, forms organic coating layer for reaction.Like this, from other sources of some organic layer or doping carbon coating layer, phosphorus atoms need not be incorporated in doping carbon coating layer.
In step 304, organic coating layer (having two-layer), understands through Overheating Treatment-carbonisation, as described in step 404.Carbonisation can about 400-1200 DEG C temperature and carry out in following any one air: argon gas, helium, nitrogen, hydrogen, carbon dioxide or its composition.In step 404, the heat of applying is by the carbonization of two organic layers (polymeric layer).In the carbonisation of step 404, organic (polymer) material is converted into codope material with carbon element, and it forms shell protective layer (metal or metalloid, nitrogen or phosphor codoping coating layer) on electrode active material 40.That is, carbonisation forms a codope carbon-coating 44 on electrode active material.In carbonisation, hydrogen, oxygen and carbon may with water (H from two organic layer coating layer electrode active material 43 (two organic coating layer metal oxide or two organic coating layer metal phosphate)
2and carbon dioxide (CO O)
2) form decompose or be evaporated.Therefore, most metals atom or metalloid atom and nitrogen or phosphorus atoms will be stayed on coating layer 44A as dopant.
It should be noted that, by selecting the compound (it forms two organic coating layer electrode active material 43) used in the chemical graft reaction of step 402 and 403, the concentration of dopant can be determined.Such as, in the organo-metallic compound selected, metal or metalloid are (for the graft reaction of step 402, to react with protonated electrode active material 41) content is higher, metal in the organic coating layer of the doping carbon (layer 44A) after two organic coating layer electrode active material 43 and carbonization or the concentration of metalloid higher, vice versa.Similarly, carry out reacting with organic coating layer electrode active material 42 in the graft reaction of step 403 and in the compound used nitrogen content higher, in the organic coating layer of the doping carbon (layer 44A) after two organic coating layer electrode active material 43 and carbonization, the concentration of nitrogen is higher, and vice versa.Equally, carry out reacting with organic coating layer electrode active material 42 in the graft reaction of step 403 and in the compound used phosphorus content higher, in the organic coating layer of the doping carbon (layer 44A) after two organic coating layer electrode active material 43 and carbonization, the concentration of phosphorus is higher, and vice versa.
As indicated by a step 404, electrode material 44 comprises electrode active material 40 and codope carbon-coating 44A.Layer 44A mainly carbon, also has metalic contamination or metalloid to ooze foreign material and N doping thing or phosphorous dopants.In other words, the main component of layer 44A is carbon.Metalloid or metal and nitrogen or phosphorus can be trace.Metalloid or metal and nitrogen-atoms or phosphorus atoms replace carbon atom on some position of layer 44A.In the embodiment of the present invention, on layer 44A, the atomic concentration of metal or metalloid is 5% or less.In the embodiment of the present invention, on layer 44A, nitrogen atom concentration is 5% or less.In the embodiment of the present invention, the compound being rich in phosphorus carbon is included in the reaction of step 403, and the phosphorus atom concentration on layer 44A is 5% or less.
In carbonisation shown in step 404, hydrogen atom, oxygen atom and some carbon atoms can be decomposed.Because the temperature being used for carrying out carbonisation is very high, organic polymer material is dehydrated or decompose.The water that hydrogen atom and oxygen atom are formed by dehydration is evaporated into steam from organic coating layer.Some carbon atoms also out form carbon dioxide from organic material decomposes.Because most of organic material is rich in carbon, after carbonisation, most of carbon is left on the surface of electrode active material 40.
Fig. 5 shows the coating layer electrode material 50 (identical with electrode material 44) of the embodiment of the present invention.Coating layer electrode material 50 is formed by process 30, as described in above step 401-404.Electrode active material 500 (identical with electrode active material 40) is by shell protective layer 501 coated (identical with layer 44A).Electrode active material 500 can comprise reactive metal oxides or metal phosphate material as LiCoO
2, LiNiO
2, LiMn
2o
4, LiFePO
4, LiNiO
2, LiNi
1/3mn
1/3co
1/3o
2, LiNi
0.5mn
0.3co
0.2o
2, xLi
2mO
3(1-x) LiMeO
2(0<x<1, M and Me are independently, and at least one is from manganese, nickel, cobalt), Fe
3o
4, SnO
2and composition.Due to the chemical reaction described in step 401-404, shell protective layer 501 is chemically bonded on electrode active material 500.Concerning a specific lithium ion battery, electrode active material 500, material coating layer can be negative material or positive electrode or both have concurrently.Shell protective layer 501 can comprise a composite construction, and it comprises (1) metal or metalloid and (2) nitrogen or phosphorus, as the co-dopant of carbon.
Shell protective layer 501 solves following two simultaneously and challenges greatly: (1) guard electrode active material 500 from the corrosive byproducts formed in lithium ionic cell unit as hydrofluoric harm; And (2) have except the protective material of defencive function except providing, and also has higher conductivity.In other words, in the embodiment of the present invention, shell protective layer 501 has dual-use function.Defencive function refers to that protective layer 501 serves as Corrosive Materia as hydrofluoric scavenger, so as can guard electrode active material 500 from erosion.Like this, shell protective layer 501 relieves the threat of unwelcome HF accessory substance.
In an embodiment of the present invention, metalic contamination or the metalloid alloy of shell protective layer 501 surround electrode active material 500, are positioned on the surface of electrode active material 500.Another function of shell protective layer 501 is; N doping thing (or phosphorous dopants) in shell protective layer 501 can improve the conductivity (compared with pure carbon) of shell protective layer 501; thus improve the conductivity of the electrode be made up of coating layer electrode material 50, improve monolithic conductive (compared with the electrode be made up of carbon coating layer with other).This is because when material with carbon element (valence state+4) is doped atom (nitrogen-atoms of such as valence state+5 or the phosphorus atoms) of higher valence state, one or more electronics from alloy (nitrogen-atoms or phosphorus atoms) can move freely, thus improve conductivity.The electric transmission that the raising of electrode conductivuty will contribute in charge/discharge process.
According to embodiments of the invention, protective layer 501 provides the stability of fabulous coating layer.Chemical bonding between electrode active material 500 (as metal oxide electrode material) and protective layer 501 contributes to the coating layer stability realizing this excellence.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 varied in thickness of protective layer 501 generated according to the embodiment of the present invention is very little.Such as, when varied in thickness is less than or equal to 20%, this layer is uniform substantially.Those skilled in the art considered that to react with the chemical graft of organic metal additive and react with the chemical graft of nitrogen and carbon source makes the thickness of protective layer 501 even.
According to embodiments of the invention; due to nonmetalloid (as nitrogen, the phosphorus) alloy of+5 valencys; the difunctional coating layer of protective layer 501 improves electric transmission; and provide material and harmfulness or corrosive byproducts simultaneously and react, prevent material from decomposing out from electrode active material 500.Although the embodiment of the present invention uses the nonmetal of+5 valencys, other nonmetal conduct+5 valency nonmetal doping agent substitute of other valence state also can be used.Therefore, the embodiment of the present invention can comprise: pre-determine the nonmetal of suitable specific valence state (valence states of such as+5 or higher), and pre-determines based on this at least in part, selects nonmetal as dopant.
The embodiment of the present invention can comprise the dopant of a type, as metal dopant, metalloid doping, N doping or phosphorus dopant.The embodiment of the present invention also can comprise the combination of dissimilar following dopant: metal dopant, metalloid dopant, nitrogen dopant, phosphorus dopant, other suitable dopants and their combination.Therefore, according to embodiments of the invention, " doping " comprises the dopant of one or more types, such as single doping-mono-dopant; Codope-two kinds of dopants, three doping-three kinds of dopants etc.
View 52 is decomposition views of protective layer 501.View 52 shows protective layer 501 and comprises the surface that metallic atom M' is located immediately at electrode active material 500.Namely metallic atom M' is in the innermost part of protective layer 501.View 52 also shows the skin that nitrogen dopant is positioned at protective layer 501.The relevant position of each dopant atom is the result of the chemical grafts reaction order of occurrence as step 402 and 403 displays.In an embodiment of the present invention, lithium ion battery (as lithium ion battery 60) comprises the electrode of the electrode active material 500 being coated with protective layer 501.Electrode (as positive pole 601) can comprise by a kind of the Li that 94% contains coating
1.2mn
0.6ni
0.2o
2the slurry that (lithium-rich anode material, LRCM), 3% acetylene carbon black and 3% Kynoar (PVDF) are dissolved in 1-METHYLPYRROLIDONE (NMP) is made.In an embodiment of the present invention, slurry is evenly coated on aluminium foil (current collector) by a kind of coating device, and by 120 DEG C of vacuumizes 12 hours, thus form electrode.Lithium ion battery 60 comprises positive pole 601, electrolyte 602, diaphragm 603 and the negative pole 600 be made up of the electrode material 50 containing coating.Positive pole 601 comprises electrode active material 500, and it is chemically bonded to protective layer 501, as mentioned above.It should be pointed out that in an embodiment of the present invention, arbitrary electrode or two electrodes can comprise coating layer as above and guard electrode active material.That is, be no matter positive pole (as negative pole 601), negative pole (such as negative pole 600) or both, all can be made up of the electrode material 50 containing coating.
Electrode material (lithium-rich anode material (LRCM) Li before and after Fig. 7 A and 7B display is coated according to the embodiment of the present invention
1.2mn
0.6ni
0.2o
2).Fig. 7 A is presented at the electrode active material before coated metalloid (silicon) nitrogen co-doped carbon.Fig. 7 B is presented at the electrode active material after coated metalloid (silicon) nitrogen co-doped carbon.The comparison of transmission electron microscope (TEM) image before and after coated shows the contrast between electrode active material and coating.In figure 7b, relatively bright region is coating, and this is the shell composite material of codope carbon (doping carbon has silicon atom (metalloid atom) and nitrogen-atoms).It should be pointed out that this coating is very uniform, there is the thickness of about 3nm.
Fig. 8 A and 8B shows the coated x-ray photoelectron power spectrum (XPS) having the electrode of silicon (metalloid)-nitrogen co-doped carbon of the embodiment of the present invention.Fig. 8 A show coated before the high-resolution Li of (solid dot) and (hollow dots) afterwards
1.2mn
0.6ni
0.2o
2the Si2p XPS spectrum of (rich lithium titanate cathode material, LRCM).Fig. 8 B show coated before the high-resolution Li of (solid dot) and (hollow dots) afterwards
1.2mn
0.6ni
0.2o
2the N1s XPS spectrum of (lithium-rich anode material, LRCM).X-ray photoelectron power spectrum (XPS) be for be determined at element (as silicon and nitrogen) in metal/metalloid-nitrogen co-doped carbon coating electrode in conjunction with energy.For the lithium-rich anode material containing coating, the formation of Si-C key in coating can be shown in the combination of 102eV.The existence of N-C key in coating lithium-rich anode material can be confirmed in the combination of 400eV.According to these results, can reach a conclusion: in metalloid-nitrogen co-doped carbon, silicon and carbon geochemistry bonding, nitrogen and carbon geochemistry bonding.The chemical bonding of such as Si-C and N-C is not detected in original lithium-rich anode material.Therefore, can to reach a conclusion, metalloid and nitrogen be by chemical bonding codope in the coating layer of carbon containing.
Fig. 9 shows the chemical impedance spectrogram before and after the lithium-rich anode material surface clad/metalloid-nitrogen co-doped carbon of the embodiment of the present invention.According to embodiments of the invention, before and after clad metal/metalloid-nitrogen co-doped carbon, carry out electrochemical impedance analysis of spectrum.As shown in the figure, before coated, the internal resistance of button cell is approximately 250 ohm, after coated, is approximately 50 ohm.Therefore, the effect that metal/metalloid-nitrogen co-doped carbon is coated is that the conductivity of electrode material increases.In one embodiment, (lithium-rich anode material, Li
1.2mn
0.6ni
0.2o
2) on be coated with silicon and nitrogen co-doped carbon-coating, the resistance variations R of the nitrogen co-doped carbon of metalloid
1/ R
00.25, wherein R
1be coated after electrode internal resistance, R
0be coated before electrode internal resistance.R
1/ R
0be worth less, show that the improvement of the internal resistance of clad material is better.
In addition, the method for the embodiment of the present invention or the product prepared by the method comprise the combination in any of following characteristics (a) to (x).The method may be used for the coated of the electrode active material of lithium ion battery.
A () carries out chemical bonding doping carbon to electrode active material.
B () doping carbon can at least doped with: (1) a kind of metal or metalloid and (2) one nonmetal, its valence state is different from the valence state (as+5 or larger valence states) of carbon.
C () chemical bonding can comprise: chemical bond unification organic layer is on electrode active material; And organic layer is converted into doping carbon.
D () chemical bond unification organic layer can comprise: the surface of protonated electrode active material, to produce hydroxyl (-OH) functional group from the teeth outwards.
E () uses an organic metal additive, metallic atom or metalloid atom to be attached on protonated surface in chemical graft mode and to form ground floor.
F carbon and non-metal source are added to described ground floor in chemical graft mode by (), to form the second layer of described organic layer.
G () is protonated can be electrode active material metal oxide or metal phosphate and are reacted containing sour organic solvent.
H the reaction of () metal oxide or metal phosphate and acid comprises: be chemically bonded to by Hydrogen Proton on metal oxide or metal phosphate.
I () metal oxide or metal phosphate can be selected from: LiCoO
2, LiNiO
2, LiMn
2o
4, LiFePO
4, LiNi
1/3mn
1/3co
1/3o
2, LiNi
0.5mn
0.3co
0.2o
2, xLi
2mO
3 (1-x) LiMeO
2(0<x<1, M and Me are independently, and at least one is from manganese, nickel, cobalt), Fe
3o
4, SnO
2, and their combination.
J () acid can be selected from: acetic acid, oxalic acid, formic acid, citric acid, and their combination.
K () organic solvent can be selected from: methyl alcohol, ethanol, isopropyl alcohol and acetone.
L metallic atom or metalloid atom are added in ground floor can comprise in chemical graft modes by (): organic metal additive and protonated surface are reacted.
M () organic metal additive can be selected from: the coupling agent of siliceous, aluminium, titanium, zirconium and their combination.
The coupling agent of (n) organic metal additive can comprise following functional group as epoxy radicals, alkoxyl and amine, comprise isopropoxy three (ethylenediamine base-N-ethyoxyl) titanate esters and 3-glycydoxy trimethoxy silane and their combination.
O () metallic atom or metalloid atom can be selected from: titanium, aluminium, silicon, tin, magnesium, zinc, zirconium and their combination.
P the inside of () ground floor can comprise described metallic atom or metalloid atom.
Q () nitrogen and carbon source can be selected from: melamine, polymine, polyacrylamide, pyrroles and its combination.
R the outermost of () second layer can comprise nitrogen and carbon source, or phosphorus and carbon source.
S () organic layer can be heat-treated in carbonisation.
T () heat treatment organic layer is heated to the temperature of 400-1200 DEG C under following atmosphere: argon gas, helium, nitrogen, hydrogen, carbon dioxide or their combination.
U () carbon can atom doped by number of different types.
V () carbon can be carbon co-doped.
W () codope carbon can comprise (1) nitrogen or phosphorus, and (2) metal or metalloid, as dopant.
X () doping carbon-coating comprises autodoping carbon.
In addition, the device of the embodiment of the present invention or system comprise following characteristics (1) to the combination in any in (11).This device or system can be lithium ion battery, the electrode of lithium ion battery or the material for the manufacture of lithium ion cell electrode.
(1) this device or system comprise electrode active material, doping carbon is had to be chemically bonded on described electrode active material, wherein this doping carbon is at least doped with (1) a kind of metal or metalloid and (2) one nonmetal, and its valence state is different from the valence state (as valence state+5 or larger valence state) of carbon.
(2) electrode active material can be selected from: metal oxide, metal sulfide, metal phosphate and their combination.
(3) innermost layer of doping carbon can comprise 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 doping carbon can comprise the nonmetal of+5 valencys.
The nonmetal of (6)+5 valencys can comprise nitrogen or phosphorus.
(7) in doping carbon, the concentration of nitrogen or phosphorus can be equal to or less than 5%.
(8) metal in doping carbon or the concentration of metalloid are equal to or less than 5%.
(9) coating layer of doping carbon to be a layer thickness be 2-50 nanometer.
(10) carbon-coating that adulterates is uniform one deck, if the thickness of this layer changes, change described in that is less than or equal to 20%.
(11) carbon-coating that adulterates comprises autodoping carbon.
The embodiment of the present invention provides a kind of method for coating, metal oxide and three-dimensional porous carbon base body is coated on the electrode material of lithium ion battery.Usually, this coating layer structure is that metal oxide is embedded in porous carbon matrix, as Figure 10 display.In final products, the percentage by weight of carbon and metal oxide is 1 ~ 10% and 0.1 ~ 1%.The thickness of coating layer is in the scope of 20 ~ 200nm.In addition, owing to using pore creating material (as surfactant), in coating layer, also loose structure can be produced.Aperture in coating layer is 2 ~ 50nm.
The embodiment of the present invention utilizes coupling agent (such as titanate coupling agents), by the electrode material surface functionalization in a solvent that suspends, then uses suitable polymer to carry out polymerization reaction, to produce polymer overmold on electrode material.Chemical bonding between coupling agent and electrode active material, make coating layer on electrode material evenly.In order to produce the carbon coating layer of porous, add pore creating material (such as surfactant) in the course of the polymerization process, this carries out at 80 DEG C, so that solvent evaporation.Then the polymer of dry jacketed electrode material, carries out carbonization subsequently in an inert atmosphere at the temperature of about 1000 DEG C.Coupling agent, polymer and surfactant are the sources of material with carbon element and metal oxide (such as titanium dioxide) particle.Metal oxide in carbon coating layer plays the effect of hydrogen fluoride (hydrogen fluoride to make performance of lithium ion battery produce decline in charge/discharge process) scavenger.Above-mentioned preparation process comprises the following steps, and shows in Fig. 10.
(1) electrode material is surface-functionalized.Electrode material (as silicon, lithium-rich anode material etc.) is evenly dispersed in (as alcohol) in organic solvent, wherein comprises organic metal coupling agent (as M=Al and Ti) for surface-functionalized.In addition, in order to form loose structure on coating layer, triblock copolymer is added as soft template.
(2) polymerization of electrode surface.Add in above-mentioned solution and there is suitable functional group (as-NH
2or epoxide group) polymer, to generate polymer on the surface at electrode active material under suitable temperature (as 80 DEG C).Polymerization process is realized by heating coupling agent and polymer.Polymer is long chain hydrocarbon, and has the functional group with coupling agent polymerization reaction take place.
(3) carbonization in an inert atmosphere.The accumulation polymer be formed on electrode active material is carried out drying, carries out carbonization subsequently.Can (as N at the temperature of 1000 DEG C and at inert atmosphere
2) middle carbonization composite material, so that metal oxide and carbon base body are coated on electrode active material.
In above-mentioned steps (1), organic metal coupling agent can be silane or zirconium coupling agent.Organic solvent for suspension electrode active material can be methyl alcohol, ethanol, acetone or toluene.In above-mentioned steps (2), the temperature of polymerization reaction can in the scope of 60 ~ 200 DEG C.In above-mentioned steps (3), carburizing temperature can be 400 ~ 2000 DEG C, and inert atmosphere can be argon gas, helium or their mixture.
The ordinary clads of electrode active material usually due to the physical mixed (as ball-milling method) in electrode material and coated source, so be the uneven coating layer of uncontrollable thickness.According to the present invention, coating thickness and composition can be controlled by the ratio changing metal oxide and carbon content in shell.And, due to the extensive chemical bonding between coupling agent and electrode active material, uniform coating layer can be produced.Therefore, the even coating layer with controlled coating thickness and composition can be realized in electrode material surface.This coating layer technology is expected to improve conductivity, and provides protection for the electrode active material of lithium ion battery.
Although described the present invention and superiority thereof in detail, should be understood that do not depart from claims definition condition of the present invention under can make various change, replacement and change.In addition, the scope of the application be not limited to describe in specification herein processing procedure, machine, manufacture, material formation, means, method and step etc. specific embodiment.The ordinary skill of this area as can be easily understood from the description, according to the present invention can utilize perform in fact to the corresponding embodiment identical function illustrated here or achieve the existing at present of identical result or the processing procedure developed in the future, machine, manufacture, material are formed, means, method and step.Therefore, appended claims is intended to comprise these processing procedures, machine, manufacture, material formation, means, method or step.
Claims (52)
1. a method for coating for the electrode active material of lithium ion battery, comprises step:
Doping carbon is coated on described electrode active material in the mode of chemical bonding, described doping carbon is at least doped with (1) a kind of metal or metalloid, (2) a kind of nonmetal, its valent state is different from the valent state of described carbon, and the step of described chemical bonding comprises:
One organic layer is chemically bonded on described electrode active material; And described organic layer is changed into described doping carbon.
2. the method for claim 1, the step wherein described organic layer being chemically bonded to described electrode active material comprises:
Protonated process is carried out on the surface of described electrode active material, to produce hydroxyl (-OH) functional group on said surface;
Organic substance containing metallic atom or metalloid atom is added to described protonated surface, to produce ground floor in chemical graft mode;
The organic substance of carbon containing and described non-metal source is added to described ground floor in chemical graft mode, to form the second layer of described organic layer.
3. method as claimed in claim 2, wherein said Protonation Step comprises:
By the metal oxide in described electrode active material or metal phosphate and, the organic solvent containing acid reacts.
4. method as claimed in claim 3, wherein comprises described metal oxide or metal phosphate and described step of carrying out reacting containing sour organic solvent: be chemically bonded to by Hydrogen Proton on described metal oxide or described metal phosphate.
5. method as claimed in claim 3, wherein said metal oxide is selected from: LiCoO
2, LiNiO
2, LiMn
2o
4, LiFePO
4, LiNi
1/3mn
1/3co
1/3o
2, LiNi
0.5mn
0.3co
0.2o
2, xLi
2mO
3(1-x) LiMeO
2(0<x<1, M and Me are independently, and at least one is from manganese, nickel, cobalt), Fe
3o
4, and SnO
2, and combination).
6. method as claimed in claim 3, wherein said acid is selected from: acetic acid, oxalic acid, formic acid, citric acid and combination thereof.
7. method as claimed in claim 3, wherein said organic solvent is selected from: methyl alcohol, ethanol, isopropyl alcohol and acetone.
8. method as claimed in claim 2, is wherein added to described protonated surface by the organic substance containing metallic atom or metalloid atom in chemical graft mode and comprises with the step producing ground floor: an organometalloid additive and described protonated surface are reacted.
9. method as claimed in claim 8, wherein said organometalloid additive is selected from: silane, aluminium, titanium, zirconium and combination thereof.
10. method as claimed in claim 8, the coupling agent of wherein said organometalloid additive comprises a functional group, it is selected from: epoxy radicals, alkoxyl and amine, comprises isopropoxy three (ethylenediamine base-N-ethyoxyl) titanate esters and 3-glycydoxy trimethoxy silane and combines.
11. methods as claimed in claim 8, wherein said metallic atom or metalloid atom are selected from titanium, aluminium, silicon, tin, magnesium, zinc, zirconium and combination thereof.
12. methods as claimed in claim 2, the inside of wherein said ground floor comprises described metallic atom or described metalloid atom.
13. methods as claimed in claim 2, wherein said carbon and non-metal source are selected from: melamine, polymine, polyacrylamide, pyrroles and combination thereof.
14. methods as claimed in claim 2, the outermost of the wherein said second layer comprises described carbon and non-metal source.
15. the method for claim 1, the step wherein described organic layer being changed into doping carbon comprises: heat-treat described organic layer in carbonisation.
16. methods as claimed in claim 15, wherein said heat treatment step comprises: described organic layer is heated to the temperature within the scope of 400 – 1200 DEG C in following atmosphere: argon gas, helium, nitrogen, hydrogen and combination thereof.
17. the method for claim 1, wherein said doping carbon has multiple different element.
18. methods as claimed in claim 17, wherein said carbon is codope carbon.
19. methods as claimed in claim 18, wherein said codope carbon comprises nitrogen or phosphorus, and metal or metalloid, as alloy.
20. the method for claim 1, wherein said doping carbon comprises autodoping carbon.
21. 1 kinds of lithium ion batteries, comprise an electrode, described electrode comprises: the electrode active material with doping carbon, described doping carbon is chemically bonded on described electrode active material, wherein said doping carbon at least doped with (1) a kind of metal or metalloid and (2) a kind of nonmetal, wherein said nonmetallic valent state is different from the valent state of carbon.
22. batteries as claimed in claim 21, wherein said electrode active material is selected from: metal oxide, metal sulfide, metal phosphate and combination thereof.
23. batteries as claimed in claim 21, the innermost layer of wherein said doping carbon comprises described metal or described metalloid.
24. batteries as claimed in claim 21, wherein said metal or described metalloid are selected from: titanium, aluminium, silicon, tin, magnesium, zinc and zirconium.
25. batteries as claimed in claim 21, the outermost layer of wherein said doping carbon comprises described nonmetal, and described nonmetallic valent state is+5.
26. batteries as claimed in claim 25, the nonmetal of wherein said valent state+5 comprises nitrogen or phosphorus.
27. batteries as claimed in claim 26, wherein said nitrogen or the concentration of phosphorus in described doping carbon are equal to or less than 5%.
28. batteries as claimed in claim 21, wherein said metal or the concentration of metalloid in described doping carbon are equal to or less than 5%.
29. batteries as claimed in claim 21, the layer thickness of wherein said doping carbon is 2 – 50nm.
30. batteries as claimed in claim 21, the layer thickness of wherein said doping carbon is uniform, if described thickness has a change, so described change is less than or equal to 20%.
31. batteries as claimed in claim 21, wherein said doping carbon comprises autodoping carbon.
32. 1 kinds for making the material of lithium ion cell electrode, described material comprises: the electrode active material with doping carbon, described doping carbon is chemically bonded on described electrode active material, wherein said doping carbon at least doped with (1) a kind of metal or metalloid and (2) a kind of nonmetal, wherein said nonmetallic valent state is different from the valent state of carbon.
33. materials as claimed in claim 32, wherein said electrode active material is selected from: metal oxide, metal sulfide, metal phosphate and combination thereof.
34. materials as claimed in claim 32, the innermost layer of wherein said doping carbon comprises described metal or described metalloid.
35. materials as claimed in claim 32, wherein said metal or described metalloid are selected from: titanium, aluminium, silicon, tin, magnesium, zinc and zirconium.
36. materials as claimed in claim 32, the outermost layer of wherein said doping carbon comprises described nonmetal, and described nonmetallic valent state is+5.
37. materials as claimed in claim 36, the nonmetal of wherein said valent state+5 comprises nitrogen or phosphorus.
38. materials as claimed in claim 37, wherein said nitrogen or the concentration of phosphorus in described doping carbon are equal to or less than 5%.
39. materials as claimed in claim 32, wherein said metal or the concentration of metalloid in described doping carbon are equal to or less than 5%.
40. materials as claimed in claim 32, the layer thickness of wherein said doping carbon is 2 – 50nm.
41. materials as claimed in claim 32, the layer thickness of wherein said doping carbon is uniform, if described thickness has a change, so described change is less than or equal to 20%.
42. materials as claimed in claim 32, wherein said doping carbon comprises autodoping carbon.
43. 1 kinds for making the product of lithium ion cell electrode, manufacturing process comprises:
Doping carbon is chemically bonded on electrode active material, wherein said doping carbon at least doped with (1) a kind of metal or metalloid and (2) a kind of nonmetal, wherein said nonmetallic valent state is different from the valent state of carbon; Wherein said chemical bonding comprises:
One organic layer is chemically bonded on described electrode active material;
Described organic layer is changed into described doping carbon.
44. products as claimed in claim 43, the step wherein an organic layer being chemically bonded to described electrode active material comprises:
By the surface protonated process of described electrode active material, to produce hydroxyl (-OH) functional group on said surface;
Organic substance containing metallic atom or metalloid atom is added to described protonated surface, to produce ground floor in chemical graft mode;
The organic substance of carbon containing and described non-metal source is added to described ground floor in chemical graft mode, to form the second layer of described organic layer.
45. products as claimed in claim 44, wherein said protonated step comprises:
By the metal oxide of described electrode active material or metal phosphate and, the organic solvent containing acid reacts.
46. products as claimed in claim 45, wherein comprise the step that described metal oxide or metal phosphate and the organic solvent containing acid carry out reacting: be chemically bonded to by Hydrogen Proton on described metal oxide or described metal phosphate.
47. products as claimed in claim 44, are wherein added to described protonated surface by the organic substance containing metallic atom or metalloid atom in chemical graft mode and comprise with the step producing ground floor: an organometalloid additive and described protonated surface are reacted.
48. products as claimed in claim 44, the inside of wherein said ground floor comprises described metallic atom or described metalloid atom.
49. products as claimed in claim 44, the outermost of the wherein said second layer comprises described carbon and non-metal source.
50. products as claimed in claim 43, the step wherein described organic layer being changed into doping carbon comprises: in carbonisation, described organic layer is heat-treated, in following atmosphere, described organic layer is heated to 400 –, 1200 DEG C of temperature: argon gas, helium, nitrogen, hydrogen and combination thereof.
51. products as claimed in claim 43, wherein said doping carbon at least autodoping has (1) nitrogen or phosphorus, and (2) metal or metalloid.
52. products as claimed in claim 43, wherein said product comprises Li
1.2mn
0.6ni
0.2o
2nano particle, and be coated with described doping carbon.
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| US14/796,816 | 2015-07-10 | ||
| US14/796,816 US20160036049A1 (en) | 2014-07-30 | 2015-07-10 | Lithium ion battery electrode material with composite functional coating |
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