CN107240684A - The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified - Google Patents

The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified Download PDF

Info

Publication number
CN107240684A
CN107240684A CN201710425517.9A CN201710425517A CN107240684A CN 107240684 A CN107240684 A CN 107240684A CN 201710425517 A CN201710425517 A CN 201710425517A CN 107240684 A CN107240684 A CN 107240684A
Authority
CN
China
Prior art keywords
positive electrode
nickelic positive
reaction
passed
reaction cavity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710425517.9A
Other languages
Chinese (zh)
Inventor
胡先罗
黄亚群
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201710425517.9A priority Critical patent/CN107240684A/en
Publication of CN107240684A publication Critical patent/CN107240684A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to secondary lithium battery field, and a kind of preparation method for the nickelic positive electrode of lithium battery that surface is modified is disclosed, including：Nickelic positive electrode powder is put into the reaction cavity of atomic layer deposition system, and reaction cavity is vacuumized into 5~10s, it is 140~160 DEG C to make reaction cavity temperature；Being passed through reaction source makes reaction cavity pressure reach 5~8mbar；It is passed through N2Take away reaction source superfluous in reaction cavity；It is passed through water to react with reaction source, sull is obtained in the surface deposition of nickelic positive electrode；It is passed through N2Take away water superfluous in reaction cavity；Repeat above step and obtain the nickelic positive electrode of lithium battery that surface is modified.Present invention also offers the nickelic positive electrode of lithium battery that the surface prepared by the above method is modified, and the anode pole piece and lithium rechargeable battery prepared by the material.The present invention has the advantages that preparation method is simple and easy to apply, coating thickness is easy to control, is adapted to large-scale production.

Description

The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified
Technical field
The invention belongs to secondary lithium battery field, the lithium battery being modified more particularly, to a kind of surface is nickelic just The preparation method and product of pole material.
Background technology
With society continuous progress, global economy be skyrocketed through it is present, scientific and technical continues to develop what is brought Product plays indispensable effect in the life of people, electronic product, electric automobile, the requirement to energy storage such as Medical Devices More and more higher, people increasingly increase the demand of the energy, and the understanding to the importance of society and economy sustainable development is constantly deep Change.Lithium ion battery is as green high-capacity rechargeable battery of new generation, since being come out from nineteen ninety, close with its voltage height, energy The outstanding advantages such as degree is big, good cycle, self discharge are small and environment-friendly, achieve fast development in nearly 20 years, are used extensively Make the power supply of pocket valuable household electrical appliance such as mobile phone, portable computer, video camera, camera etc., current lithium-ion electric Pond positive electrode mainly includes cobalt acid lithium, LiFePO4, nickelic positive electrode etc..
However, further investigations have shown that, in lithium ion battery, because the potential residing for positive electrode is higher, and de- lithium State positive electrode has stronger oxidisability, easily occurs side reaction with organic electrolyte, so that deteriorating the performance of battery.Although Nickel system positive electrode LiNiO2Due to having the advantages that specific discharge capacity is high, cheap, but its some intrinsic defect Limit its extensive use：Such as measure the LiNiO of ratio2Be difficult to synthesize, exist in discharge process more dephasign become, Ni2+Occupy Li+ 3a positions cause cation mixing, high nickel content very strong in latter stage of charging catalytic activity, easy catalytic electrolysis liquid is decomposed, room temperature and Storge quality is poor, in addition, nickelic positive electrode have that first circle is inefficient in charge and discharge process and cyclic process in by Unstable rock salt phase is transformed into by stable layer structure in structure, causes the problem of cycle performance is poor.
Due to there is drawbacks described above and deficiency, this area, which is needed badly, makes further perfect and changes to nickelic positive electrode Enter, solve the problem of its cycle performance present in charge and discharge process is poor.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the lithium battery being modified the invention provides a kind of surface is nickelic The preparation method of positive electrode and the material, the preparation method is with reference to the nickelic positive electrode performance characteristics of itself, using atom Layer deposition techniques carry out surface coating modification to nickelic positive electrode, obtain the nickelic positive electrode of lithium ion of surface modification, enter And the material manufacture lithium rechargeable battery is used, thus obtained lithium rechargeable battery can overcome nickelic positive electrode filling In discharge process the problem of capacity attenuation, its structural stability and cycle performance are greatly improved, and the surface of the application is modified in addition The nickelic positive electrode of lithium battery also have preparation method is simple and easy to apply, coating thickness is easy to control, be adapted to large-scale production etc. Advantage.
To achieve the above object, according to one aspect of the present invention, it is proposed that the lithium battery that a kind of surface is modified is nickelic just The preparation method of pole material, comprises the following steps：
(a) nickelic positive electrode powder is put into the reaction cavity of atomic layer deposition system, and by the reaction cavity 5s~10s is vacuumized, the nickelic positive electrode is LiNixCoyMzO2, wherein 0.6≤x≤1,0≤y≤0.4,0≤z≤ 0.4, and x+y+z=1, M are the one or more in Mn, Al, Mg, Ti；Raise the temperature of the reaction cavity so that temperature is protected Hold at 140 DEG C~160 DEG C；
(b) reaction source is passed through into the reaction cavity, and causes the pressure in reaction cavity to reach 5mbar~8mbar, The reaction source is adsorbed on the surface of the nickelic positive electrode powder；
(c) it is passed through N into the reaction cavity2, to take away reaction source superfluous in the reaction cavity, the time of being passed through is 120s~150s；
(d) continue to be passed through H into the reaction cavity2O, until the pressure of the reaction cavity reaches 5mbar~8mbar When stop be passed through, the H2The reaction sources of the O with absorption on the nickelic positive electrode surface reacts, with described nickelic The surface deposition of positive electrode obtains sull；
(e) and then into the reaction cavity it is passed through N2, to take away the byproduct of reaction and surplus in the reaction cavity H2O, is passed through the time for 120s~150s；
(f) repeat step (b)~(e) obtains the nickelic positive pole material of lithium battery that the surface with required deposit thickness is modified Material.
As it is further preferred that the reaction source is one kind in metallorganic, metal simple-substance and metal halide； The metallic element used in the metallorganic, metal simple-substance and metal halide is one kind in Ti, Al, Fe, Zn.
It is another aspect of this invention to provide that the nickelic positive electrode of lithium battery being modified there is provided a kind of surface, it is by described Method prepare.
It is another aspect of this invention to provide that there is provided a kind of anode pole piece, the anode pole piece includes collector and coating The nickelic positive electrode of lithium battery that surface described on the collector is modified.
As it is further preferred that the anode pole piece also include conductive agent and binding agent, the conductive agent, binding agent and It is coated in after the nickelic positive electrode three mixing of lithium battery that surface is modified on the collector.
As it is further preferred that the surface be modified the nickelic positive electrode of lithium battery, conductive agent, binding agent mixing Ratio is：Surface be modified the nickelic positive electrode of lithium battery mass fraction be 50~99.5wt%, conductive agent be 0.1~ 40wt%, binding agent is 0.1~40wt%.
As it is further preferred that the conductive agent is carbon black, acetylene black, native graphite, CNT, graphene, carbon One or more in fiber；The binding agent is polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamides One kind or many in amine, polypropylene, polyvingl ether, polyimides, SB, sodium carboxymethylcellulose Kind.
It is another aspect of this invention to provide that there is provided a kind of lithium rechargeable battery, it includes described anode pole piece.
As it is further preferred that also including cathode pole piece, barrier film, electrolyte and battery case.
As it is further preferred that the barrier film is preferably aramid fiber barrier film, nonwoven cloth diaphragm, polyethene microporous membrane, poly- third One kind in alkene film, polypropylene-polyethylene bilayer or sandwich diaphragm, ceramic coating layer barrier film；The electrolyte includes electrolyte And solvent, the electrolyte is preferably LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)、LiBOB、 One or more in LiCl, LiBr, LiI；The solvent is preferably propylene carbonate (PC), dimethyl carbonate (DMC), carbon Sour methyl ethyl ester (EMC), 1,2- dimethoxy-ethanes (DME), ethylene carbonate, propene carbonate, butylene, carbonic acid diethyl One or more in ester, methyl propyl carbonate, acetonitrile, ethyl acetate, ethylene sulfite.
In general, possess following compared with prior art, mainly by the contemplated above technical scheme of the present invention Technological merit：
1. preparation method of the present invention, using ALD to the nickelic positive electrode carry out table for preparing anode Face is modified, and method is simple to operation, can be coated on a large scale, and compared with the conventional method, the uniformity coefficient of clad More preferably, the thickness of clad is more preferably controlled.
During 2. the present invention is modified on surface, by the key parameter control such as reaction temperature, reaction time and reaction pressure System within the specific limits, can effectively improve the effect of surface modification, while the reaction speed that surface is modified is improved, so that most The performance of thus lithium rechargeable battery prepared by nickelic positive electrode is improved eventually.
3. preparation method of the present invention, has selected transition metal oxide such as TiO2To enter to nickelic positive electrode Row surface treatment, has carried out surface modification treatment to nickelic positive electrode by simple several steps, has simplified whole preparation The flow of method, high efficiency, obtains positive electrode to be prepared in high quality, and whole preparation process be easy to operation and Quality control, especially for surface coated control particularly simple and easy to apply.
Brief description of the drawings
Fig. 1 is a kind of flow chart of the preparation method of the nickelic positive electrode of lithium battery of surface modification of the present invention；
Fig. 2 is the X-ray powder diffraction of the nickelic positive electrode of uncoated nickelic positive electrode and cladding different-thickness (XRD) collection of illustrative plates；
Fig. 3 (a) and Fig. 3 (b) are SEM (SEM) figures of uncoated nickelic positive electrode；
Fig. 3 (c) and Fig. 3 (d) are SEM (SEM) figures for the nickelic positive electrode that the present invention is coated；
Fig. 4 (a) is the TEM figures of uncoated nickelic positive electrode；Fig. 4 (b) is the nickelic positive electrode that the present invention is coated Transmission electron microscope (TEM) figure；
Fig. 5 (a) is the first circle of the battery of the nickelic positive electrode of uncoated nickelic positive electrode and cladding different-thickness Charging and discharging curve；
Fig. 5 (b) is the circulation of the battery of the nickelic positive electrode of uncoated nickelic positive electrode and cladding different-thickness Performance map；
Fig. 5 (c) is uncoated nickelic positive electrode and the nickelic positive electrode battery coated under different current densities High rate performance；
Fig. 5 (d) is nickelic positive electrode battery the putting under different multiplying of uncoated nickelic positive electrode and cladding Electric curve.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below Not constituting conflict each other can just be mutually combined.
The principle of the present invention is in positive electrode surface depositing metal oxide film, by this using atomic layer deposition method Plant method of modifying and result in more uniform clad, and can effectively control the thickness of clad, by coating table Face film can effectively completely cut off the erosion of many material surfaces of electrolyte, improve the structural stability of overall material.
As shown in figure 1, a kind of preparation method for the nickelic positive electrode of lithium battery being modified the invention provides surface, including Following steps：
(a) nickelic positive electrode is put into the anti-of ALD (Atomic layer deposition, ald) system Answer in cavity, and reaction cavity is vacuumized into 5s~10s, nickelic positive electrode is LiNixCoyMzO2, wherein 0.6≤x≤1,0 ≤ y≤0.4,0≤z≤0.4, and x+y+z=1, M are the one or more in Mn, Al, Mg, Ti, raise the temperature of reaction cavity Degree so that reaction temperature remains at 140 DEG C~160 DEG C；
(b) be passed through reaction source in the reaction cavity to after vacuumizing, and cause the pressure in reaction cavity reach 5mbar~ 8mbar, the reaction source is adsorbed on the surface of the nickelic positive electrode；
(c) it is passed through N into the reaction cavity2, to take away reaction source superfluous in the reaction cavity, the time of being passed through is 120s~150s；
(d) continue to be passed through H into the reaction cavity2O, terminates to be passed through when chamber pressure reaches 5mbar~8mbar H2O, because the temperature in reaction cavity is 140 DEG C~160 DEG C, the water being passed through is changed into vapor at such a temperature, vapor with Adsorb the reaction source on nickelic positive electrode surface to react, with thin in the surface of nickelic positive electrode deposition monoxide Byproduct of reaction can be produced in film, course of reaction, specific accessory substance will not be described here；
(e) and then into reaction cavity it is passed through N2, to take away the byproduct of reaction in the reaction cavity and superfluous H2O, The time is passed through for 120s~150s；
(f) repeat step (b)~(e) obtains the nickelic positive pole material of lithium battery that the surface with required deposit thickness is modified Material.
Specifically, the reaction source of deposition is one kind in metallorganic, metal simple-substance and metal halide, wherein, gold It is one kind in Ti, Al, Fe, Zn to belong to element.Above-mentioned reaction source has following feature：1) reaction source has sufficiently high steam Pressure, fully can cover and fill the surface of matrix material；2) reaction source has preferable stability, will not occur selfdecomposition, Will not etched the matrix material；3) reaction source has certain chemism, can be rapidly in material surface formation chemisorbed, energy It is enough to reach that saturation is adsorbed in a short time.
Present invention also offers a kind of anode pole piece, the anode pole piece include collector and be coated on the collector by The nickelic positive electrode of the lithium battery prepared by the inventive method.
Further, the anode pole piece also includes conductive agent and binding agent, and the conductive agent, binding agent and lithium battery are nickelic It is coated in after positive electrode three mixing on the collector.
It is preferred that, the nickelic positive electrode of lithium battery, conductive agent, the mixed proportion of binding agent are：The nickelic positive pole material of lithium battery The mass fraction of material is 50~99.5wt%, and conductive agent is 0.1~40wt%, and binding agent is 0.1~40wt%, more comparison Experiment shows that the anode pole piece prepared using the mass ratio has more excellent chemical property.
It is further preferred that the conductive agent is carbon black, acetylene black, native graphite, CNT, graphene, carbon fiber In one or more；The binding agent is polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, poly- One or more in propylene, polyvingl ether, polyimides, SB, sodium carboxymethylcellulose.
Present invention also offers a kind of lithium rechargeable battery, it includes the positive pole pole prepared by the inventive method Piece.
Specifically, the lithium rechargeable battery also includes cathode pole piece, barrier film, electrolyte and battery case.
It is preferred that, the barrier film is aramid fiber barrier film, nonwoven cloth diaphragm, polyethene microporous membrane, polypropylene screen, the poly- second of polypropylene One kind in alkene bilayer or sandwich diaphragm, ceramic coating layer barrier film.
It is further preferred that electrolyte includes electrolyte and solvent, electrolyte is preferably LiPF6、LiBF4、LiClO4、 LiAsF6、LiCF3SO3、LiN(CF3SO2), the one or more in LiBOB, LiCl, LiBr, LiI；Solvent is preferably propylene Carbonic ester (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), 1,2- dimethoxy-ethanes (DME), ethylene carbonate, One in propene carbonate, butylene, diethyl carbonate, methyl propyl carbonate, acetonitrile, ethyl acetate, ethylene sulfite Plant or a variety of.
It is below the specific embodiment of the present invention.
Embodiment 1
Using ALD equipment in nickelic positive electrode LiNiO2Surface depositing Ti O2Film, reaction source is H2O and isopropyl titanium, Depositing temperature is 150 DEG C.By nickelic positive electrode LiNiO2It is put into the reaction chamber in ALD, deposition process is as follows：(1) will Reaction chamber vacuumizes 5s；(2) reaction titanium source (isopropyl titanium) is passed through so that chamber pressure reaches 5mbar；(3) into reaction system It is passed through N2, the time is 120s, for taking away the accessory substance and superfluous isopropyl titanium of reaction；(4) continue to be passed through into reaction chamber H2O, terminates when chamber pressure reaches 5mbar；(5) N is passed through into reaction system2, the time is 120s, for taking away reaction Accessory substance and superfluous H2O；Step (1)~(5) are a deposited intact process, and cycle-index is 20 times.
Embodiment 2
Using ALD equipment in nickelic positive electrode LiNi0.6Co0.4O2Surface deposits ZnO film, and reaction source is H2O and ZnCl2, depositing temperature is 150 DEG C.By nickelic positive electrode LiNi0.6Co0.4O2It is put into the reaction chamber in ALD, deposition process It is as follows：(1) reaction chamber is vacuumized into 6s；(2) it is passed through reaction zinc source (ZnCl2) cause chamber pressure to reach 6mbar；(3) to anti- Answer and N is passed through in system2, the time is 130s, for taking away the accessory substance and superfluous zinc chloride of reaction；(4) continue to reaction chamber Inside it is passed through H2O, terminates when chamber pressure reaches 6mbar；(5) N is passed through into reaction system2, the time is 140s, for taking away The accessory substance of reaction and superfluous H2O；Step (1)~(5) are a deposited intact process., cycle-index is 25 times.
Embodiment 3
Using ALD equipment in nickelic positive electrode LiNi0.4Co0.2Mn0.4O2Surface depositing Al 2O3 films, reaction source is H2O And metallic aluminium, depositing temperature is 150 DEG C.By nickelic positive electrode LiNi0.4Co0.2M0.4O2It is put into the reaction chamber in ALD, Deposition process is as follows：(1) reaction chamber is vacuumized into 10s；(2) reaction silicon source (aluminium simple substance) is passed through so that chamber pressure reaches 8mbar；(3) N is passed through into reaction system2, the time is 150s, for taking away the accessory substance and superfluous metallic aluminium of reaction；(4) Continue to be passed through H into reaction chamber2O, terminates when chamber pressure reaches 8mbar；(5) N is passed through into reaction system2, the time is 150s, for taking away the accessory substance and superfluous H of reaction2O；Step (1)~(5) are a deposited intact process, cycle-index For 30 times.
Embodiment 4
Using ALD equipment in nickelic positive electrode LiNi0.5Co0.3Al0.2O2Surface deposits Fe2O3Film.Reaction source is H2O And FeCl3, depositing temperature is 150 DEG C.By nickelic positive electrode LiNi0.5Co0.3M0.2O2It is put into the reaction chamber in ALD, sinks Product process is as follows：(1) reaction chamber is vacuumized into 7s；(2) it is passed through reaction source of iron (FeCl3) cause chamber pressure to reach 7mbar； (3) N is passed through into reaction system2, the time is 140s, for taking away the accessory substance and superfluous FeCl of reaction3；(4) continue to anti- Intracavitary is answered to be passed through H2O, terminates when chamber pressure reaches 7mbar；(5) N is passed through into reaction system2, the time is 130s, is used for Take away the accessory substance and superfluous H of reaction2O；Step (1)~(5) are a deposited intact process, and cycle-index is 20 times.
Embodiment 5
Using ALD equipment in nickelic positive electrode LiNi0.6Ti0.4O2Surface depositing Ti O2Film, reaction source is H2O and TiCl4, depositing temperature is 150 DEG C.By nickelic positive electrode LiNi0.6Ti0.4O2It is put into the reaction chamber in ALD, deposition process It is as follows：(1) reaction chamber is vacuumized into 5s；(2) it is passed through reaction titanium source (TiCl4) cause chamber pressure to reach 5mbar；(3) to anti- Answer and N is passed through in system2, the time is 130s, for taking away the accessory substance and superfluous TiCl of reaction4；(4) continue into reaction chamber It is passed through H2O, terminates when chamber pressure reaches 6mbar, and (5) are passed through N into reaction system2, the time is 120s, anti-for taking away The accessory substance and superfluous H answered2O；Step (1)~(5) are a deposited intact process, and cycle-index is 25 times.
Embodiment 6
Using ALD equipment in nickelic positive electrode LiNi0.5Co0.3Mg0.2O2Surface depositing Ti O2Film, reaction source is H2O And Titanium, depositing temperature is 150 DEG C.By nickelic positive electrode LiNi0.5Co0.3Mg0.2O2It is put into the reaction chamber in ALD, Deposition process is as follows：(1) reaction chamber is vacuumized into 10s；(2) reaction titanium source (Titanium) is passed through so that chamber pressure reaches 5mbar；(3) N is passed through into reaction system2, the time is 150s, for taking away the accessory substance and superfluous Titanium of reaction；(4) Continue to be passed through H into reaction chamber2O, terminates when chamber pressure reaches 6mbar, and (5) are passed through N into reaction system2, the time is 150s, for taking away the accessory substance and superfluous H of reaction2O；Step (1)~(5) are a deposited intact process, cycle-index For 30 times.
Embodiment 7
Nickelic positive electrode and conductive agent carbon black and polyfluortetraethylene of binding element prepared by embodiment 1 is according to a certain percentage Mixing, wherein the mass fraction ratio of positive electrode are 50%, and the mass fraction ratio of conductive agent is 30%, the mass fraction of binding agent Than for 20%, a certain amount of NMP (1-METHYLPYRROLIDONE) can be added in order to adjust slurry concentration, it is well mixed after be coated in aluminium On paper tinsel collector.
Embodiment 8
Nickelic positive electrode and conductive agent native graphite and binding agent polyacrylic acid prepared by embodiment 2 is according to certain ratio Example mixing, wherein the mass fraction ratio of positive electrode are 75%, and the mass fraction ratio of conductive agent is 15%, the quality point of binding agent Number adds a certain amount of NMP than being 10%, is coated in after being well mixed in aluminum foil current collector.
Embodiment 9
Nickelic positive electrode and conductive agent graphene and binding agent polypropylene prepared by embodiment 3 is mixed according to a certain percentage Close, wherein the mass fraction ratio of positive electrode is 99.5%, the mass fraction ratio of conductive agent is 0.1%, the quality point of binding agent Number adds a certain amount of NMP than being 0.4%, is coated in after being well mixed in aluminum foil current collector.
Embodiment 10
Nickelic positive electrode and conductive agent carbon black and binding agent polyamide prepared by embodiment 4 is mixed according to a certain percentage Close, wherein the mass fraction ratio of positive electrode is 50%, the mass fraction ratio of conductive agent is 40%, the mass fraction ratio of binding agent For 10%, and add a certain amount of NMP, it is well mixed after be coated in aluminum foil current collector.
Embodiment 11
Nickelic positive electrode and conductive agent carbon black and polyfluortetraethylene of binding element prepared by embodiment 5 is according to a certain percentage Mixing, wherein the mass fraction ratio of positive electrode are 40%, and the mass fraction ratio of conductive agent is 20%, the mass fraction of binding agent Than for 40%, and add a certain amount of NMP, it is well mixed after be coated in aluminum foil current collector.
Embodiment 12
Nickelic positive electrode and conductive agent carbon black and binding agent polypropylene prepared by embodiment 6 is mixed according to a certain percentage Close, wherein the mass fraction ratio of positive electrode is 99%, the mass fraction ratio of conductive agent is 0.9%, the mass fraction of binding agent Than for 0.1%, and add a certain amount of NMP, it is well mixed after be coated in aluminum foil current collector.
Embodiment 13
Anode pole piece prepared by embodiment 7 makes 2032 type button cells, wherein, battery case is stainless steel material, is born Pole pole piece uses lithium metal, and barrier film is Celgard 2300, and electrolyte is 1.0mol/LLiPF6, solvent is EC/DMC systems.
Embodiment 14
Anode pole piece prepared by embodiment 8 makes 2032 type button cells, wherein, battery case is stainless steel material, Cathode pole piece uses sodium metal, and barrier film is fibreglass diaphragm, and electrolyte is 1.0mol/LLiPF4, solvent is EMC/DMC bodies System.
Embodiment 15
Anode pole piece prepared by embodiment 9 makes 2032 type button cells, wherein, battery case is stainless steel material, is born Pole pole piece uses lithium metal, and barrier film is aramid fiber barrier film, and electrolyte is 1.0mol/LLiASF6, solvent is EC/PC systems.
Embodiment 16
Anode pole piece prepared by embodiment 10 makes 2032 type button cells, wherein, battery case is stainless steel material, is born Pole pole piece uses potassium metal, and barrier film is ceramic coating layer barrier film, and electrolyte is 1.0mol/LLiCl, and solvent is EC/DMC systems.
Embodiment 17
Anode pole piece prepared by embodiment 11 makes 2032 type button cells, wherein, battery case is stainless steel material, is born Pole pole piece uses sodium metal, and barrier film is nonwoven cloth diaphragm, and electrolyte is 1.0mol/LLiCl, and solvent is PC/DMC systems.
Embodiment 18
Anode pole piece prepared by embodiment 12 makes 2032 type button cells, wherein, battery case is stainless steel material, is born Pole pole piece uses potassium metal, and barrier film is polypropylene-polyethylene double-layered compound film, and electrolyte is 1.0mol/LLiBOB, and solvent is carbon Vinyl acetate.
Fig. 2 is that cladding different-thickness prepared by uncoated NCA (nickelic positive electrode) powder and the embodiment of the present invention 1 is thin The XRD spectrum (cladding thickness is respectively 2nm, 4nm, 6nm) of the nickelic positive electrode of film, cladding process can be analyzed using XRD In whether introduce impurity and determine coating composition.As can be seen that the present invention is changed using ALD progress surface from XRD spectrum Property, the structure change of NCA materials is not caused, all obvious diffraction maximums correspond to α-NaFeO2Structure, wherein dividing Obvious I (006)/I (102) peaks and I (018)/I (110) peak illustrate that the material after cladding remains in that good two Tie up layer structure.In addition, not occurring TiO in XRD collection of illustrative plates2Diffraction maximum, be primarily due to deposition thickness in 2nm ~6nm, TiO2Content it is relatively low therefore do not detect TiO2Presence.Therefore, ALD does not change NCA crystal structure And composition.
Fig. 3 is that uncoated NCA and the SEM for carrying out the NCA after surface modification by cladding scheme, wherein Fig. 3 (a) and Fig. 3 (b) before for cladding, Fig. 3 (c) and Fig. 3 (d) are after coating.It can be seen that cladding before and after NCA particles remain in that it is spherical Pattern, granular size is about 5~10 μm, and whole spheric granules is made up of primary grains, and primary grains are irregular particle, from The presence of clad can not be found out in SEM figures, in order to further determine that clad, ALD surfaces bag is further analyzed using TEM The change for the material surface structure that coated tape comes.
Fig. 4 is uncoated NCA and Surface coating such as TiO2The NCA of clad TEM figures, because coating thickness is 4nm, it is impossible to the presence of clad, therefore the observation particle table that can be become apparent from using TEM are directly observed from SEM figures The pattern change in face.As can be seen that uncoated NCA particle surfaces are smooth and smooth from Fig. 4 (a), and utilize ALD claddings TiO2Afterwards, rough has obvious clad, and shown in such as Fig. 4 (b), the thickness of clad is about 4nm, default with ALD Thickness it is basically identical, illustrate that the thickness of clad can be controlled very well using ALD.
In order to study influence of the ALD deposition clad to NCA, in 1C (180mA g-1) current density under to of the invention real The battery for applying the preparation of example 13 carries out constant current charge-discharge test, and voltage range is 2.8~4.3V, and test temperature is 25 DEG C, and it is tested As a result it is as shown in Figure 5.
Fig. 5 (a) is uncoated NCA and ALD-2 (cladding thickness is 2nm), ALD-4 (cladding thickness is 4nm), ALD-6 The first circle charging and discharging curve of battery prepared by (cladding thickness is 6nm), wherein abscissa are specific discharge capacity, and ordinate is electricity Pressure, as can be seen from the figure coat before and after prepare battery charging and discharging curve it is similar, discharge voltage plateau in 3.7V or so, And first circle discharge capacity is respectively 161.5mAh g-1、160.7mAh g-1、173.5mAh g-1、165.2mAh g-1, discharge capacity Do not have greatly changed, first circle efficiency is 71.5%, 79.3%, 78.7% and 73.7% respectively.After cladding NCA first circle efficiency is above uncoated NCA, and when the thickness of clad increases to 6nm, the trend of reduction is presented in first circle efficiency.
Fig. 5 (b) is the cycle performance figure of battery prepared by uncoated NCA and ALD-2, ALD-4, ALD-6, wherein horizontal sit It is designated as circulating the number of turns, ordinate is specific discharge capacity.In the cyclic process of discharge and recharge, the discharge capacity in former circles of circulation It is slightly elevated, it is to be caused by the activation of material.As can be seen from the figure ALD-4 cycle performance is better than other samples, not The NCA of cladding is after 100 circle charge and discharge cycles, and discharge capacity is only 141.8mAh g-1, capability retention 87.8%, ALD-2 is after 100 circle charge and discharge cycles, and discharge capacity is 155.2mAh g-1, capability retention 96.5%, ALD-4 processes After 100 circle charge and discharge cycles, discharge capacity is 169.0mAh g-1, capability retention 97.4%, ALD-6 is by 100 circle discharge and recharges After circulation, discharge capacity is 149.7mAh g-1, capability retention 90.6%.From experimental result as can be seen that after cladding NCA cycle performance has obtained big lifting, and particularly when the thickness of clad is 4nm, capability retention is lifted from 87.8% To 97.4%, while discharge capacity is not reduced also, but when the thickness of clad brings up to 6nm, capacity is kept under starting Drop, this is probably that can hinder Li because the thickness of the clad when material surface is too thick+Diffusion, therefore optimal clad Thickness is 4nm.
Fig. 5 (c) is high rate performance of the batteries that prepare of uncoated NCA and ALD-2 under different current densities, wherein horizontal Coordinate is the circulation number of turns, and ordinate is specific discharge capacity.NCA before cladding is under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C Discharge capacity be respectively 180.2mAh g-1, 183mAh g-1, 174.6mAh g-1, 166.7mAh g-1, 157.4mAh g-1, 136.5mAh g-1With 103.9mAh g-1, it can be seen that under the current density of big multiplying power, uncoated NCA electrochemistry Can be poor, illustrate that the polarization of material is more serious, and ALD-2 specific discharge capacities under identical current density are respectively 193.2mAh g-1, 190.4mAh g-1, 181.3mAh g-1, 174.2mAh g-1, 165.4mAh g-1, 150.2mAh g-1With 128.9mAh g-1, the NCA after Surface coating has good high rate performance, and this explanation clad can be to a certain degree The degree of polarization of upper reduction material.
Fig. 5 (d) is discharge curves of the NCA under different multiplying before and after coating, and wherein abscissa is specific discharge capacity, is indulged Coordinate is voltage, it is also seen that with the increase of current density, the NCA after cladding reduces voltage attenuation from figure Degree, thus can also illustrate that NCA materials under clad effect, can reduce polarization of the material in charge and discharge process and ask Topic.
Therefore, represent that the structure of nickelic positive electrode can be improved through Surface coating by efficient and good cycle performance Stability, so as to improve the cycle performance of nickelic positive electrode.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include Within protection scope of the present invention.

Claims (10)

1. the preparation method for the nickelic positive electrode of lithium battery that a kind of surface is modified, it is characterised in that comprise the following steps：
(a) nickelic positive electrode powder is put into the reaction cavity of atomic layer deposition system, and the reaction cavity is taken out very Empty 5s~10s, the nickelic positive electrode is LiNixCoyMzO2, wherein 0.6≤x≤1,0≤y≤0.4,0≤z≤0.4, and x + y+z=1, M are the one or more in Mn, Al, Mg, Ti；Raise the temperature of the reaction cavity so that temperature is maintained at 140 DEG C~160 DEG C；
(b) reaction source is passed through into the reaction cavity, and causes the pressure in reaction cavity to reach 5mbar~8mbar, this is anti- Source absorption is answered on the surface of the nickelic positive electrode powder；
(c) it is passed through N into the reaction cavity2, to take away reaction source superfluous in the reaction cavity, the time is passed through for 120s ~150s；
(d) continue to be passed through H into the reaction cavity2O, until the pressure of the reaction cavity stops when reaching 5mbar~8mbar Only it is passed through, the H2The reaction sources of the O with absorption on the nickelic positive electrode surface reacts, with the nickelic positive pole The surface deposition of material obtains sull；
(e) and then into the reaction cavity it is passed through N2, to take away the byproduct of reaction in the reaction cavity and superfluous H2O, The time is passed through for 120s~150s；
(f) repeat step (b)~(e) obtains the nickelic positive electrode of lithium battery that the surface with required deposit thickness is modified.
2. the preparation method for the nickelic positive electrode of lithium battery that surface as claimed in claim 1 is modified, it is characterised in that described Reaction source is one kind in metallorganic, metal simple-substance and metal halide；The metallorganic, metal simple-substance and metal The metallic element used in halide is one kind in Ti, Al, Fe, Zn.
3. the nickelic positive electrode of lithium battery that a kind of surface is modified, it is characterised in that as described in claim any one of 1-2 It is prepared by method.
4. a kind of anode pole piece, it is characterised in that the anode pole piece include collector and be coated on the collector such as power Profit requires the nickelic positive electrode of lithium battery that the surface described in 3 is modified.
It is the conductive agent, viscous 5. anode pole piece as claimed in claim 4, it is characterised in that also including conductive agent and binding agent It is coated in after the nickelic positive electrode three mixing of lithium battery that knot agent and surface are modified on the collector.
6. anode pole piece as claimed in claim 5, it is characterised in that the nickelic positive electrode of lithium battery of the surface modification, Conductive agent, the mixed proportion of binding agent are：The mass fraction for the nickelic positive electrode of lithium battery that surface is modified for 50~ 99.5wt%, conductive agent is 0.1~40wt%, and binding agent is 0.1~40wt%.
7. anode pole piece as claimed in claim 6, it is characterised in that the conductive agent be carbon black, acetylene black, native graphite, One or more in CNT, graphene, carbon fiber；The binding agent is polytetrafluoroethylene (PTFE), polyvinylidene fluoride, poly- ammonia Ester, polyacrylic acid, polyamide, polypropylene, polyvingl ether, polyimides, SB, carboxymethyl cellulose One or more in plain sodium.
8. a kind of lithium rechargeable battery, it is characterised in that including the anode pole piece as any one of claim 4-7.
9. lithium rechargeable battery as claimed in claim 8, it is characterised in that also including cathode pole piece, barrier film, electrolyte and Battery case.
10. lithium rechargeable battery as claimed in claim 9, it is characterised in that the barrier film is preferably aramid fiber barrier film, nonwoven In cloth diaphragm, polyethene microporous membrane, polypropylene screen, polypropylene-polyethylene bilayer or sandwich diaphragm, ceramic coating layer barrier film It is a kind of；The electrolyte includes electrolyte and solvent, and the electrolyte is preferably LiPF6、LiBF4、LiClO4、LiAsF6、 LiCF3SO3、LiN(CF3SO2), the one or more in LiBOB, LiCl, LiBr, LiI；The solvent is preferably propylene carbon Acid esters (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), 1,2- dimethoxy-ethanes (DME), ethylene carbonate, carbon One kind in acid propylene ester, butylene, diethyl carbonate, methyl propyl carbonate, acetonitrile, ethyl acetate, ethylene sulfite Or it is a variety of.
CN201710425517.9A 2017-06-08 2017-06-08 The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified Pending CN107240684A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710425517.9A CN107240684A (en) 2017-06-08 2017-06-08 The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710425517.9A CN107240684A (en) 2017-06-08 2017-06-08 The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified

Publications (1)

Publication Number Publication Date
CN107240684A true CN107240684A (en) 2017-10-10

Family

ID=59986175

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710425517.9A Pending CN107240684A (en) 2017-06-08 2017-06-08 The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified

Country Status (1)

Country Link
CN (1) CN107240684A (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108987695A (en) * 2018-07-11 2018-12-11 武汉艾特米克超能新材料科技有限公司 Preparation method, positive electrode, positive plate and the lithium battery of positive electrode material precursor
CN109980183A (en) * 2017-12-27 2019-07-05 中国电子科技集团公司第十八研究所 Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment
CN110048111A (en) * 2019-04-25 2019-07-23 柔电（武汉）科技有限公司 Cell positive material, battery anode slice and lithium battery
CN110165141A (en) * 2018-02-13 2019-08-23 大众汽车有限公司 The active material of cathode of electrochemical apparatus and method for active material of cathode coating
CN110993887A (en) * 2019-12-31 2020-04-10 恩创动力设备(南京)有限公司 Preparation method of metal oxide coated lithium ion battery anode
CN111082025A (en) * 2019-12-31 2020-04-28 恩创动力设备(南京)有限公司 Preparation method of atomic layer deposition coated high-nickel ternary cathode material
CN111172510A (en) * 2020-01-07 2020-05-19 杭州电子科技大学 High-nickel ternary cathode material Al2O3Chemical vapor deposition preparation method of/Al composite modified layer
CN112186189A (en) * 2020-09-30 2021-01-05 东莞力朗电池科技有限公司 Binder for high-nickel ternary material positive plate, positive plate and battery
CN112531147A (en) * 2020-12-03 2021-03-19 珠海冠宇电池股份有限公司 Positive active material and preparation method and application thereof
WO2021115469A1 (en) * 2019-12-13 2021-06-17 华中科技大学 Method for preparing lithium-ion battery material
CN113889620A (en) * 2017-10-26 2022-01-04 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN114156478A (en) * 2021-11-30 2022-03-08 厦门韫茂科技有限公司 Anode material coated with co-embedded film, preparation method and lithium ion battery
EP4040523A1 (en) * 2021-02-03 2022-08-10 Imec VZW Coated cathode
CN114927665A (en) * 2022-06-07 2022-08-19 宁波容百新能源科技股份有限公司 Composite cathode material and preparation method thereof
CN115432751A (en) * 2022-10-25 2022-12-06 格林美股份有限公司 Modified positive electrode material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102244231A (en) * 2010-05-14 2011-11-16 中国科学院物理研究所 Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery
CN105648422A (en) * 2016-01-14 2016-06-08 北京大学深圳研究生院 Gaseous phase atomic layer deposition device for electrode powder material coating and application
KR20160100854A (en) * 2015-02-16 2016-08-24 한양대학교 에리카산학협력단 Cathode active material powder for lithium secondary battery and manufacturing method of the same
CN106207130A (en) * 2016-08-31 2016-12-07 华中科技大学 A kind of lithium battery nickelic positive electrode of surface modification and preparation method thereof
CN106384838A (en) * 2016-11-03 2017-02-08 上海空间电源研究所 Atomic layer deposition modified lithium-ion battery and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102244231A (en) * 2010-05-14 2011-11-16 中国科学院物理研究所 Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery
KR20160100854A (en) * 2015-02-16 2016-08-24 한양대학교 에리카산학협력단 Cathode active material powder for lithium secondary battery and manufacturing method of the same
CN105648422A (en) * 2016-01-14 2016-06-08 北京大学深圳研究生院 Gaseous phase atomic layer deposition device for electrode powder material coating and application
CN106207130A (en) * 2016-08-31 2016-12-07 华中科技大学 A kind of lithium battery nickelic positive electrode of surface modification and preparation method thereof
CN106384838A (en) * 2016-11-03 2017-02-08 上海空间电源研究所 Atomic layer deposition modified lithium-ion battery and preparation method thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113889620A (en) * 2017-10-26 2022-01-04 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN109980183A (en) * 2017-12-27 2019-07-05 中国电子科技集团公司第十八研究所 Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment
CN110165141A (en) * 2018-02-13 2019-08-23 大众汽车有限公司 The active material of cathode of electrochemical apparatus and method for active material of cathode coating
CN108987695A (en) * 2018-07-11 2018-12-11 武汉艾特米克超能新材料科技有限公司 Preparation method, positive electrode, positive plate and the lithium battery of positive electrode material precursor
CN110048111A (en) * 2019-04-25 2019-07-23 柔电（武汉）科技有限公司 Cell positive material, battery anode slice and lithium battery
WO2021115469A1 (en) * 2019-12-13 2021-06-17 华中科技大学 Method for preparing lithium-ion battery material
CN110993887A (en) * 2019-12-31 2020-04-10 恩创动力设备(南京)有限公司 Preparation method of metal oxide coated lithium ion battery anode
CN111082025A (en) * 2019-12-31 2020-04-28 恩创动力设备(南京)有限公司 Preparation method of atomic layer deposition coated high-nickel ternary cathode material
CN111172510B (en) * 2020-01-07 2022-03-22 杭州电子科技大学 High-nickel ternary cathode material Al2O3Chemical vapor deposition preparation method of/Al composite modified layer
CN111172510A (en) * 2020-01-07 2020-05-19 杭州电子科技大学 High-nickel ternary cathode material Al2O3Chemical vapor deposition preparation method of/Al composite modified layer
CN112186189A (en) * 2020-09-30 2021-01-05 东莞力朗电池科技有限公司 Binder for high-nickel ternary material positive plate, positive plate and battery
CN112531147A (en) * 2020-12-03 2021-03-19 珠海冠宇电池股份有限公司 Positive active material and preparation method and application thereof
EP4040523A1 (en) * 2021-02-03 2022-08-10 Imec VZW Coated cathode
WO2022167356A1 (en) * 2021-02-03 2022-08-11 Imec Vzw Coated cathode
CN114156478A (en) * 2021-11-30 2022-03-08 厦门韫茂科技有限公司 Anode material coated with co-embedded film, preparation method and lithium ion battery
CN114156478B (en) * 2021-11-30 2023-09-05 厦门韫茂科技有限公司 Positive electrode material coated with co-embedded film, preparation method and lithium ion battery
CN114927665A (en) * 2022-06-07 2022-08-19 宁波容百新能源科技股份有限公司 Composite cathode material and preparation method thereof
CN115432751A (en) * 2022-10-25 2022-12-06 格林美股份有限公司 Modified positive electrode material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN107240684A (en) The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified
EP3316356B1 (en) Anode material having a porous core-shell structure and preparation method thereof, and battery
CN109950620B (en) Non-aqueous electrolyte for lithium ion battery and lithium ion battery
CN104617259B (en) The protection processing of cathode of lithium in lithium secondary battery
CN102044670A (en) Negative active material and method of preparing the same, and rechargeable lithium battery
US20110171529A1 (en) Electrode active material, method for producing same, electrode for nonaqueous secondary battery, and nonaqueous secondary battery
CN107331853B (en) Graphene composite multilayer porous spherical lithium manganate electrode material and lithium ion battery prepared from same
CN102456881B (en) Olivine type phosphate cathode material and preparation method thereof as well as positive electrode and battery both containing olivine type phosphate cathode material
CN107112528A (en) Positive active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery
KR20120056674A (en) Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
CN107834050A (en) A kind of lithium-enriched cathodic material of lithium ion battery and its improved method
US11611074B2 (en) Cathode active material for lithium secondary battery, method for manufacturing same, and lithium secondary battery comprising same
CN106207130A (en) A kind of lithium battery nickelic positive electrode of surface modification and preparation method thereof
CN110581277B (en) Surface coating method of lithium ion battery anode material
CN108604675A (en) Include the positive active material for lithium secondary battery and preparation method thereof of high voltage lithium and cobalt oxides
CN107431249A (en) The manufacture method of rechargeable nonaqueous electrolytic battery
CN108807928B (en) Synthesis of metal oxide and lithium ion battery
CN110635116A (en) Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery
CN110048111A (en) Cell positive material, battery anode slice and lithium battery
CN112467121A (en) Positive plate and preparation method and application thereof
KR20110027324A (en) Cathode active material with improved performance for lithium secondary battery, manufacturing method thereof and lithium secondary battery comprising the same
CN108598411B (en) Nitrogen-doped carbon-coated tin oxide/iron oxide composite material, preparation method thereof and lithium battery material
CN111244563A (en) Positive electrode lithium ion supplement additive and preparation method and application thereof
CN102956891A (en) Preparation method of lithium ion battery cathode active material Fe3O4/C, cathode and lithium ion battery
CN100466343C (en) Anode active material compsns anode sheet and Li ion cell

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20171010