CN110212182A - Cell positive material and the positive plate comprising it, cell negative electrode material and the negative electrode tab comprising it, lithium ion battery and electrode slurry - Google Patents
Cell positive material and the positive plate comprising it, cell negative electrode material and the negative electrode tab comprising it, lithium ion battery and electrode slurry Download PDFInfo
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- CN110212182A CN110212182A CN201910443944.9A CN201910443944A CN110212182A CN 110212182 A CN110212182 A CN 110212182A CN 201910443944 A CN201910443944 A CN 201910443944A CN 110212182 A CN110212182 A CN 110212182A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/36—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
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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
- H01M4/48—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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
Abstract
The present invention relates to a kind of cell positive material, including positive electrode active materials, positive electrode binder, positive conductive agent and nano inorganic oxide, the positive electrode active materials are ternary material, and the ternary material is nickle cobalt lithium manganate, chemical formula LiNixCoyMn1‑x‑ yO2, 0 < x < 1,0 < y < 1.The invention further relates to a kind of cell negative electrode material, including negative electrode active material, negative electrode binder, cathode conductive agent and nano inorganic oxide, the negative electrode active material is graphite.The invention further relates to a kind of positive plate, a kind of negative electrode tab, a kind of lithium ion battery and a kind of electrode slurrys.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of cell positive material and include its anode
Piece, cell negative electrode material and the negative electrode tab comprising it, lithium ion battery and electrode slurry.
Background technique
Lithium ion battery has high energy density and operating voltage, is all efficient energy-storage travelling wave tube and electricity all the time
System can be discharged.But with the development of technology and industry requirement, the lithium ion battery of more preferable energy density by there is an urgent need to.Lithium from
The energy density of sub- battery is determined that improving its operating voltage is to improve battery energy density by the capacity of operating voltage and material
The method of one simple possible, but corresponding battery side reaction aggravation, electrolyte decomposition under high voltage, are caused electric under high voltage
The cyclical stability in pond is very poor, and there is greatly security risk.
With the increasingly developed of lithium ion battery and application, it is concerned by people and payes attention to further.Explore high-voltage electricity
Solution additive is solved, preferably electrolyte prescription is an important channel for solving lithium ion battery cyclical stability.In addition, current needle
It further include modified to positive battery negative electrode material or ceramics to the research that lithium ion battery cyclical stability and security performance improve
Diaphragm coating etc., higher cost, and also to production technology, higher requirements are also raised.
Summary of the invention
Based on this, it is necessary to provide a kind of cell positive material and the positive plate comprising it, cell negative electrode material and comprising
Its negative electrode tab and lithium ion battery.
The present invention provides a kind of cell positive material, including positive electrode active materials, positive electrode binder, positive conductive agent and
Nano inorganic oxide, the positive electrode active materials are ternary material, and the ternary material is nickle cobalt lithium manganate, and chemical formula is
LiNixCoyMn1-x-yO2, 0 < x < 1,0 < y < 1.
The nano inorganic oxide includes Nano-meter SiO_2 in one of the embodiments,2, nano-ZnO, nanometer Cu2O, it receives
Rice CuO, nanometer Al2O3, nano-TiO2One of or it is a variety of.
The nano inorganic oxide includes nano-ZnO, nanometer Cu in one of the embodiments,2O, in nanometer CuO
It is one or more.
It is furthermore preferred that the nano inorganic oxide is nanometer Cu2O。
The content of the nano inorganic oxide is the cell positive material total weight in one of the embodiments,
0.5% to 5%, preferably 0.5% to 3%.
The particle size of the nano inorganic oxide is 10nm to 50nm in one of the embodiments,.
The nano inorganic oxide is the oxygen-starved metal oxide with Lacking oxygen in one of the embodiments,.
The positive electrode binder includes polyvinylidene fluoride, polytetrafluoroethylene (PTFE) and gathers inclined in one of the embodiments,
One of difluoroethylene-hexafluoropropene is a variety of；The positive conductive agent includes conductive carbon black, one in oiliness carbon nanotube
Kind is a variety of.
The present invention provides a kind of positive plate, the cell positive material including plus plate current-collecting body and on plus plate current-collecting body
Layer, the cell positive material layer is the coat formed by the cell positive material.
The present invention provides a kind of cell negative electrode material, including negative electrode active material, negative electrode binder, cathode conductive agent and
Nano inorganic oxide, the negative electrode active material are graphite.
The nano inorganic oxide includes Nano-meter SiO_2 in one of the embodiments,2, nano-ZnO, nanometer Cu2O, it receives
Rice CuO, nanometer Al2O3, nano-TiO2One of or it is a variety of.
The content of the nano inorganic oxide is that the lithium ion battery negative material is total in one of the embodiments,
The 0.5% to 5% of weight, preferably 0.5% to 3%.
The particle size of the nano inorganic oxide is 10nm to 50nm in one of the embodiments,.
The negative electrode binder includes one of butadiene-styrene rubber, polyacrylonitrile or a variety of in one of the embodiments,；
The cathode conductive agent includes one of conductive carbon black, aqueous carbon nanotube or a variety of；The cell negative electrode material further includes
Thickener, it is preferred that the thickener is sodium carboxymethylcellulose.
The present invention provides a kind of negative electrode tab, the cell negative electrode material including negative current collector and on negative current collector
Layer, the cell negative electrode material layer is the coat formed by the cell negative electrode material.
It is described the present invention also provides a kind of lithium ion battery, including positive plate, negative electrode tab, lithium battery diaphragm and electrolyte
Positive plate is the positive plate and/or the negative electrode tab is the negative electrode tab.
The present invention further provides a kind of electrode slurrys, comprising:
The cell positive material or the cell negative electrode material；And
Organic solvent, the organic solvent and the cell positive material or the cell negative electrode material are mixed to form slurry
Shape mixture.
Cell positive material or cell negative electrode material provided by the invention are added with nano inorganic oxide, can effectively mention
The high positive or negative pole material interface stability of battery.Nano inorganic oxide and electrolyte have compatibility, can promote electrolyte
Wetting improves the electrolyte adsorption capacity of positive or negative pole material and protects liquid measure, improves charge and discharge uniformity, and then improve battery
Cycle performance.In addition, inorganic nanometer oxide also has the function of micro-moisture in Electolyte-absorptive, to be further reduced electricity
Corrosion during the recycling of pond to positive electrode, improves the stability of the positive electrode.Nanometer is added in negative electrode material
Inorganic oxide can also effectively improve the consistency of SEI film.
Detailed description of the invention
Fig. 1 is the cycle performance test data curve graph of battery in test example of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, by the following examples, it and combines attached
Figure, the present invention is described in more detail.It should be appreciated that described herein, specific examples are only used to explain the present invention, and
It is not used in the restriction present invention.
A kind of cell positive material, including positive electrode active materials, positive electrode binder, positive conductive agent and nano inorganic oxygen
Compound, the positive electrode active materials are ternary material, and the ternary material is nickle cobalt lithium manganate, and chemical formula is
LiNixCoyMn1-x-yO2, 0 < x < 1,0 < y < 1.
Cell positive material provided in an embodiment of the present invention as positive electrode active materials and is added using cobalt nickel lithium manganate ternary material
Added with nano inorganic oxide, cell positive material interface stability can be effectively improved.In addition, inorganic nanometer oxide also has
The effect of micro-moisture in Electolyte-absorptive, so that it is further reduced the corrosion in circulating battery use process to positive electrode,
Improve the stability of the positive electrode.
The example of the nano inorganic oxide is specifically as follows Nano-meter SiO_22, nano-ZnO, nanometer Cu2O, nanometer CuO, receive
Rice Al2O3, nano-TiO2.Preferably, the nano inorganic oxide includes nano-ZnO, nanometer Cu2O, one of nanometer CuO
Or it is a variety of, it is furthermore preferred that the nano inorganic oxide is nanometer Cu2O。
In one embodiment, the content of the nano inorganic oxide is the 0.5% of the cell positive material total weight
To 5%, further, preferably 0.5% to 3%.The cell positive material total weight is the positive electrode active materials, anode
The sum of binder, positive conductive agent and weight of nano inorganic oxide.
In the content range, the nano inorganic oxide can be evenly distributed on the ternary material surface, to described
Ternary material forms effective cladding, due to the property of the nano inorganic oxide, is coated on the institute on the ternary material surface
One layer of protective layer can be formed by stating nano inorganic oxide, improved the structural stability of the cell positive material, effectively prevent electricity
Erosion during the recycling of pond to positive electrode.Simultaneously because packet of the nano inorganic oxide to the ternary material
It covers, can also slow down the rate of anode release oxygen during circulating battery, avoid battery that thermal runaway occurs, effectively improve cell safety
Property.
The content of the nano inorganic oxide is too low or the excessively high performance for being unfavorable for improving the cell positive material.
If the content of nano inorganic oxide described in the cell positive material is too low, also can not effectively with the ternary material shape
At protective layer；If the too high levels of nano inorganic oxide described in the cell positive material will affect the embedding of lithium ion
Enter abjection.
In one embodiment, the particle size of the nano inorganic oxide is 10nm to 50nm.The particle size range
Interior inorganic oxide nanoparticle is easier to coat the positive electrode active materials formation protective layer.
In one embodiment, the nano inorganic oxide is the oxygen-starved metal oxide with Lacking oxygen, it is preferred that
Including oxygen-starved nano-ZnO, oxygen-starved nanometer Cu2O, oxygen-starved nanometer CuO, more preferably oxygen-starved nanometer Cu2O.The anoxic
Type metal oxide has oxygen absorption function, and the oxygen of anode release can be absorbed when thermal runaway occurs for battery, reaches and stablizes anode
Effect, further increases battery security.The source of the oxygen-starved metal oxide is not limited specifically, commercially available to obtain
Obtaining conventionally voluntarily to prepare.
The positive electrode active materials nickle cobalt lithium manganate may include LiNi0.6Co0.2Mn0.2O2(NCM622 type),
LiNi0.5Co0.2Mn0.3O2(NCM523 type), LiNi0.4Co0.2Mn0.4O2(NCM424 type) and LiNi1/3Co1/3Mn1/3O2
It is one of (NCM111 type) or a variety of, preferably LiNi0.6Co0.2Mn0.2O2(NCM622 type).
The specific type of the positive electrode binder is unlimited, as long as cementation can be played.Preferably, the anode
Binder can be selected from one of polyvinylidene fluoride, polytetrafluoroethylene (PTFE) and polyvinylidene fluoride-hexafluoropropene or a variety of.
In one embodiment, the content of the positive electrode binder be the cell positive material total weight 1% to
1.5%, further, the content of the positive electrode binder be preferably the cell positive material total weight 1.1% to
1.3%.
The specific type of the positive conductive agent is also unlimited, can be selected according to actual needs.Preferably, the anode
Conductive agent can be selected from one of conductive carbon black, superconduction carbon black, electrically conductive graphite, acetylene black, oiliness carbon nanotube or a variety of.Into one
Step, the positive conductive agent includes conductive carbon black and oiliness carbon nanotube.
In one embodiment, the content of the positive conductive agent is the 2% to 3% of the cell positive material total weight,
Further, the content of the positive conductive agent is preferably the 2.5% to 3% of the cell positive material total weight.
The embodiment of the present invention also provides a kind of cell negative electrode material, including negative electrode active material, negative electrode binder, cathode are led
Electric agent and nano inorganic oxide, the negative electrode active material are graphite.
Cell negative electrode material provided in an embodiment of the present invention as negative electrode active material and is added with nano inorganic oxygen using graphite
Compound can effectively improve cell negative electrode material interface stability.Nano inorganic oxide and electrolyte have compatibility, can promote
The wetting of electrolyte improves the electrolyte adsorption capacity of negative electrode material and protects liquid measure, and then it is uniform to improve negative electrode material charge and discharge
Property, improve the consistency for forming SEI film, improves the cyclical stability of battery.
The example of the nano inorganic oxide is specifically as follows Nano-meter SiO_22, nano-ZnO, nanometer Cu2O, nanometer CuO, receive
Rice Al2O3, nano-TiO2。
In one embodiment, the content of the nano inorganic oxide is the 0.5% of the cell negative electrode material total weight
To 5%, further, preferably 0.5% to 3%.The cell negative electrode material total weight is the negative electrode active material, cathode
The sum of binder, cathode conductive agent and weight of nano inorganic oxide.
If the content of nano inorganic oxide described in the cell negative electrode material is too low, cathode can not be effectively improved
The electrolyte adsorption capacity and guarantor's liquid measure of material, are also unable to improve the consistency to form SEI film；If in the cell negative electrode material
The too high levels of the nano inorganic oxide then will affect the insertion abjection of lithium ion.
The specific type of the negative electrode binder is unlimited, as long as cementation can be played.Preferably, the bonding
Agent can be selected from one of butadiene-styrene rubber and polyacrylonitrile or a variety of.
In one embodiment, the content of the negative electrode binder is the 2% to 3% of the cell negative electrode material total weight,
Further, the content of the negative electrode binder is preferably the 2.5% to 3% of the cell negative electrode material total weight.
In one embodiment, the cell negative electrode material further includes thickener, and the type of the thickener is unlimited, such as carboxylic
Sodium carboxymethylcellulose pyce can be used as preferred thickener and be added in the cell negative electrode material.In the cell negative electrode material, institute
The content for stating thickener is 0.5% to 1.5% of weight in the cell negative electrode material.Further, the thickener
Content is 1% to 1.5% of weight in the cell negative electrode material.
The specific type of the cathode conductive agent is also unlimited, can be selected according to actual needs.Preferably, the cathode
Conductive agent can be selected from one of conductive carbon black, superconduction carbon black, electrically conductive graphite, acetylene black, aqueous carbon nanotube or a variety of.Into one
Step, the cathode conductive agent includes conductive carbon black and aqueous carbon nanotube.
In one embodiment, the content of the cathode conductive agent be the cell negative electrode material total weight 1.5% to
2.5%, further, the content of the cathode conductive agent is preferably the 2% to 2.5% of the cell negative electrode material total weight.
The embodiment of the present invention also provides a kind of positive plate and a kind of negative electrode tab, and the positive plate includes plus plate current-collecting body and position
In the cell positive material layer on plus plate current-collecting body, the cell positive material layer is the battery provided in an embodiment of the present invention
The coat that positive electrode is formed；The negative electrode tab includes negative current collector and the cell negative electrode material on negative current collector
Layer, the cell negative electrode material layer are the coat that the cell negative electrode material provided in an embodiment of the present invention is formed.
In one embodiment, the plus plate current-collecting body or the negative current collector are metal material, and specific type can basis
Actual demand is selected, for example, aluminium foil, aluminium net can be used as plus plate current-collecting body, copper foil, copper mesh can be used as negative pole currect collecting
Body.
In the embodiment of the present invention, the preparation method of the positive plate and the negative electrode tab is not particularly limited, can be according to
It is prepared by conventional method.For example, the method including following two step is selected to prepare the positive plate or the cathode
Piece.
S20, by the positive or negative pole active material, positive or negative pole binder, positive or negative pole conductive agent and nano inorganic
Oxide is added in solvent and is mixed, and is uniformly mixed and obtains positive or negative pole slurry；The solvent can be selected from water or N- methyl
Pyrrolidines.
The positive or negative pole slurry is uniformly coated on positive or negative pole collector by S40, after drying, roll-in, slitting,
Obtain the positive or negative pole piece.Wherein, the dry temperature of the anode sizing agent is preferably 80 DEG C to 85 DEG C, the negative electrode slurry
Dry temperature is preferably 105 DEG C -110 DEG C.In addition, the condition of roll-in and slitting is configured according to conventional.
In order to enable the nano inorganic oxide uniformly to coat the positive or negative pole active material, it is preferred that step
S20 includes:
S22 mixes the nano inorganic oxide and the positive or negative pole active material；
The positive or negative pole conductive agent is added into the mixed material of step S22 and is mixed by S24, add it is described just
Or negative electrode binder is mixed, and is eventually adding the solvent, such as the positive solvent is deionization, the cathode solvent is
N- crassitude, is mixed.
It is furthermore preferred that in the step S24, it is described that the step of solvent is mixed is added at 45 DEG C to 55 DEG C
It is carried out under heating condition.
In addition, the thickener of aforementioned selection can also be added together when adding the negative electrode binder.
In step S20, the positive or negative pole active material, positive or negative pole binder, positive or negative pole conductive agent, thickener with
And the additive amount of nano inorganic oxide is added according to aforementioned each corresponding content of substance.The amount of the solvent is according to
The total weight of the positive or negative pole material of battery is selected, and guarantees that the solid content of the anode sizing agent is 60% to 65%, described negative
Solid content is 40% to 45% in the slurry of pole.
The embodiment of the present invention further provides for a kind of lithium ion battery, including positive plate, negative electrode tab, lithium battery diaphragm and electricity
Solve liquid, wherein at least one in the positive plate and the negative electrode tab is positive plate provided in an embodiment of the present invention or cathode
Piece.Specific combination can include:
1, a kind of lithium ion battery, including the positive plate provided in an embodiment of the present invention, common negative electrode tab, lithium battery every
Film and electrolyte；
2, a kind of lithium ion battery, including common positive plate, the negative electrode tab provided in an embodiment of the present invention, lithium battery every
Film and electrolyte；
3, a kind of lithium ion battery, including it is the positive plate provided in an embodiment of the present invention, provided in an embodiment of the present invention
The negative electrode tab, lithium battery diaphragm and electrolyte.
The type of the lithium battery diaphragm and the electrolyte is unlimited, and any routine used in lithium ion battery can be selected
The electrolyte of lithium battery diaphragm material and routine；It does not include the nothing in the common positive plate and the common negative electrode tab
Machine nano-oxide, specific type can be unlimited.
The preparation of 1 positive plate of embodiment
S00 provides nano inorganic oxide (oxygen-starved nanometer Cu2O, partial size 20nm), ternary material
(LiNi0.6Co0.2Mn0.2O2), positive electrode binder (Kynoar, PVDF), conductive agent 1 (conductive carbon black SP), conductive agent 2 (oil
Property carbon nanotube), content is respectively 0.5%, 95.5%, 1.3%, 2%, the 0.7% of total solid quality；
Solvents N-methyl pyrrolidines is added in substance each in step S00 by S20, and anode sizing agent, solid content is made in mixing
It is 60%；
S40 is coated on aluminum foil current collector (16 μm of thickness), positive plate is made.
The preparation of 2 negative electrode tab of embodiment
S00 provides nano inorganic oxide (oxygen-starved nano Si2O, partial size 20nm), negative electrode active material (graphite),
Conductive agent 1 (conductive carbon black SP), conductive agent 2 (aqueous carbon nanotube), thickener (sodium carboxymethylcellulose), negative electrode binder
(butadiene-styrene rubber, SBR), content are respectively 0.5%, 93.6%, 1.3%, 0.7%, 1.1%, the 2.8% of total solid quality；
Solvent deionized water is added in substance each in step S00 by S20, and negative electrode slurry is made in mixing, and solid content is
41%；
S40 is coated on copper foil current collector (9 μm of thickness), negative electrode tab is made.
Comparative example 1
S00 provides ternary material (LiNi0.6Co0.2Mn0.2O2), positive electrode binder (Kynoar, PVDF), conductive agent
1 (conductive carbon black SP), conductive agent 2 (oiliness carbon nanotube), content be respectively total solid quality 96%, 1.3%, 2%,
0.7%；
Solvents N-methyl pyrrolidines is added in substance each in step S00 by S20, and anode sizing agent, solid content is made in mixing
It is 60%；
S40 is coated on aluminum foil current collector (16 μm of thickness), positive plate is made.
Comparative example 2
S00, provide negative electrode active material (graphite), conductive agent 1 (conductive carbon black SP), conductive agent 2 (aqueous carbon nanotube),
Thickener (sodium carboxymethylcellulose), negative electrode binder (butadiene-styrene rubber, SBR), content is respectively total solid quality
94.1%, 1.3%, 0.7%, 1.1%, 2.8%；
Solvent deionized water is added in substance each in step S00 by S20, and negative electrode slurry is made in mixing, and solid content is
41%；
S40 is coated on copper foil current collector (9 μm of thickness), negative electrode tab is made.
Test example
By positive plate prepared by embodiment 1 and negative electrode tab prepared by comparative example 2 through roll-in, slitting, film-making, winding, encapsulation,
Battery 01 is made in the processing steps such as fluid injection, chemical conversion, partial volume.
By negative electrode tab prepared by embodiment 2 and positive plate prepared by comparative example 1 through roll-in, slitting, film-making, winding, encapsulation,
Battery 02 is made in the processing steps such as fluid injection, chemical conversion, partial volume.
By positive plate prepared by comparative example 1 and negative electrode tab prepared by comparative example 2 through roll-in, slitting, film-making, winding, encapsulation,
Battery 03 is made in the processing steps such as fluid injection, chemical conversion, partial volume.
Above-mentioned battery 01-03 is tested according to following conditions respectively, charge and discharge range when test is 3.0-
4.2V, specifically:
1, all batteries are subjected to initialization charging at room temperature according to the following steps before test:
(1) battery is according to 0.2C electric current (600mA) constant-current constant-voltage charging to charge cutoff voltage 4.2V, cut-off current
0.02C(60mA)；
(2) battery is according to 0.2C current discharge to discharge cut-off voltage 3V, and 3. battery is filled according to 0.2C electric current constant current constant voltage
Electricity is to charge cutoff voltage 4.2V, cut-off current 0.02C.
The discharge capacity of recording step (2) is C0。
2, circulating battery cycle performance is tested, and steps are as follows:
(1) battery is according to 0.2C electric current (600mA) constant-current constant-voltage charging to charge cutoff voltage 4.2V, cut-off current
0.02C(60mA)；
(2) battery is according to 0.2C current discharge to discharge cut-off voltage 3V.It is recycled according to above-mentioned steps.As a result as schemed
Shown in 1.
3, high-temperature storage performance is tested, and steps are as follows:
1) 85 DEG C of -4h shelve test
(1) battery of initialization charging stores 4h at 85 DEG C；
(2) at room temperature, battery is according to 0.2C current discharge to discharge cut-off voltage 3V；
(3) battery is according to 0.2C electric current constant-current constant-voltage charging to charge cutoff voltage 4.2V, cut-off current 0.02C；
(4) at room temperature, battery is according to 0.2C current discharge to discharge cut-off voltage 3V.
The discharge capacity of recording step (2) and step (4) is respectively C1、C2.Calculate its capacity retention ratio=C1/C0, capacity
Recovery rate=C2/C0.As a result such as table 1.
1 85 DEG C of -4h test results of table
2), 60 DEG C of -7d shelve test
(1) battery of initialization charging shelves 7d at 60 DEG C；
(2) at room temperature, battery is according to 0.2C current discharge to discharge cut-off voltage 3V；
(3) battery is according to 0.2C electric current constant-current constant-voltage charging to charge cutoff voltage 4.2V, cut-off current 0.02C；
(4) at room temperature, battery is according to 0.2C current discharge to discharge cut-off voltage 3V.
The discharge capacity of recording step (2) and step (4) is respectively C3、C4.Calculate its capacity retention ratio=C3/C0, capacity
Recovery rate=C4/C0.As a result such as table 2.
2 60 DEG C of -7d test results of table
From the point of view of test result, the stability and cycle performance of battery 01 and battery 02 are superior to battery 03.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (16)
1. a kind of cell positive material, which is characterized in that including positive electrode active materials, positive electrode binder, positive conductive agent and
Nano inorganic oxide, the positive electrode active materials are ternary material, and the ternary material is nickle cobalt lithium manganate, and chemical formula is
LiNixCoyMn1-x-yO2, 0 < x < 1,0 < y < 1.
2. cell positive material according to claim 1, which is characterized in that the nano inorganic oxide includes nanometer
SiO2, nano-ZnO, nanometer Cu2O, nanometer CuO, nanometer Al2O3, nano-TiO2One of or it is a variety of.
3. cell positive material according to claim 1, which is characterized in that the nano inorganic oxide includes nanometer
ZnO, nanometer Cu2O, one of nanometer CuO or a variety of.
4. cell positive material according to claim 1, which is characterized in that the content of the nano inorganic oxide is institute
State the 0.5% to 5% of cell positive material total weight.
5. anode material for lithium-ion batteries according to claim 1, which is characterized in that the grain of the nano inorganic oxide
Diameter size is 10nm to 50nm.
6. cell positive material according to claim 1, which is characterized in that the nano inorganic oxide is with oxygen sky
The oxygen-starved metal oxide of position.
7. cell positive material according to claim 1, which is characterized in that the positive electrode binder includes gathering inclined difluoro second
One of alkene, polytetrafluoroethylene (PTFE) and polyvinylidene fluoride-hexafluoropropene are a variety of；The positive conductive agent includes conductive carbon
One of black, oiliness carbon nanotube is a variety of.
8. a kind of positive plate, which is characterized in that the cell positive material layer including plus plate current-collecting body and on plus plate current-collecting body,
The cell positive material layer is the coat formed by the described in any item cell positive materials of claim 1~7.
9. a kind of cell negative electrode material, which is characterized in that including negative electrode active material, negative electrode binder, cathode conductive agent and
Nano inorganic oxide, the negative electrode active material are graphite.
10. cell negative electrode material according to claim 9, which is characterized in that the nano inorganic oxide includes nanometer
SiO2, nano-ZnO, nanometer Cu2O, nanometer CuO, nanometer Al2O3, nano-TiO2One of or it is a variety of.
11. cell negative electrode material according to claim 9, which is characterized in that the content of the nano inorganic oxide is
The 0.5% to 5% of the lithium ion battery negative material total weight.
12. cell negative electrode material according to claim 9, which is characterized in that the partial size of the nano inorganic oxide is big
Small is 10nm to 50nm.
13. cell negative electrode material according to claim 9, which is characterized in that the negative electrode binder include butadiene-styrene rubber,
One of polyacrylonitrile is a variety of；The cathode conductive agent includes one of conductive carbon black, aqueous carbon nanotube or a variety of；
The cell negative electrode material further includes thickener, it is preferred that the thickener is sodium carboxymethylcellulose.
14. a kind of negative electrode tab, which is characterized in that the cell negative electrode material including negative current collector and on negative current collector
Layer, the cell negative electrode material layer is the coat formed by the described in any item cell negative electrode materials of claim 9~13.
15. a kind of lithium ion battery, which is characterized in that including positive plate, negative electrode tab, lithium battery diaphragm and electrolyte, it is described just
Pole piece is the positive plate according to any one of claims 8 and/or the negative electrode tab is negative electrode tab described in the claim 14.
16. a kind of electrode slurry characterized by comprising
Described in any item cell positive materials or according to the described in any item electricity of claim 9~13 according to claim 1~7
Pond negative electrode material；And
It is mixed that organic solvent, the organic solvent and the cell positive material or the cell negative electrode material are mixed to form pulp-like
Close object.
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