CN108258193A - A kind of negative plate and preparation method thereof, lithium ion battery - Google Patents
A kind of negative plate and preparation method thereof, lithium ion battery Download PDFInfo
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- CN108258193A CN108258193A CN201711462814.7A CN201711462814A CN108258193A CN 108258193 A CN108258193 A CN 108258193A CN 201711462814 A CN201711462814 A CN 201711462814A CN 108258193 A CN108258193 A CN 108258193A
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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
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of 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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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 invention belongs to field of lithium ion battery, are related to a kind of negative plate, including negative current collector and are attached to the negative electrode material layer on negative current collector surface, negative electrode material layer includes the first negative electrode material layer and the second negative electrode material layer；First negative electrode material layer is attached to the surface of negative current collector, first negative electrode material layer includes the first material sections and in the second material sections of the first material area edge, the thickness of first material sections is more than the thickness of the second material sections, second negative electrode material layer is attached to the surface of the second material sections, and the second negative electrode material layer is in the edge of the first negative electrode material layer.Present invention reduces traditional negative plate because edge-coating amount is relatively low, the risk of battery short circuit caused by Li dendrite is easily generated, reduces the probability of happening of lithium ion battery safety accident, improves the security performance of lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of negative plate and preparation method thereof and packet
Include the lithium ion battery of the negative plate.
Background technology
Lithium ion battery has been taken the lead in since the nineties by Sony Corporation of Japan since commercialization, with its high-energy density, Gao Xun
Ring service life, low self-discharge performance are widely applied in electronic field.With industry and economic fast development, oil supplies
The pollution problem of contradiction and environment is needed to become increasingly conspicuous, various countries are one after another using development new-energy automobile as national strategy.Nearest three
Year, the utilization rate of domestic new-energy automobile is in hot growth, and new-energy automobile uses lithium ion battery, so as to drive
The volume of production and marketing sharp increase of lithium ion battery.
The capacity of lithium ion battery being loaded on new-energy automobile is big, and voltage is high, and the capacity of loading is big, new to support with this
Energy automobile runs enough mileages.It is known that the capacity of lithium ion battery is higher, voltage is higher, and energy is higher, thus
The security risk brought is higher, therefore lithium ion battery is to pay close attention in new-energy automobile product and worry the most the most safely
Problem.
There are many factor for causing lithium ion battery safety accident, specifically include the super-charge super-discharge of lithium ion battery, inside and outside
Short circuit, heat abuse, Li dendrite, shock and needle thorn etc..Wherein since short circuit caused by Li dendrite is that lithium ion battery uses process
In the problem of paying close attention to the most, to prevent the above problem, lithium ion battery must stringent management and control during designing and producing.
The generation of the Li dendrite of lithium ion battery in order to prevent, the measure that lithium ion battery uses in design include the capacity of negative plate
Beyond the capacity certain proportion or negative plate of positive plate certain width wider than positive plate etc..In the actual production process, lithium from
The pole piece (positive plate and negative plate) of sub- battery come coating sizing-agent, makes marginal flow of the slurry to pole piece using extrusion coater
Prolong, the edge thickness for often leading to pole piece in this way is partially thin, and partially thin width is differed for 1~10mm.And the partially thin field capacity deviates
Design value, cause negative plate capacity be less than corresponding face positive plate capacity, due to the deficiency of the capacity of negative plate, easily
Li dendrite is formed on negative plate, leads to battery short circuit so as to bring the security risk of lithium ion battery.Although tune can be passed through
The means such as the characteristic of whole slurry and the painting parameter of coating die head that adjusts coating machine reduce partially thin region, but still cannot disappear
Except generating the phenomenon that partially thin on negative plate；And the consistency of slurry and the stability of coating machine are difficult to ensure that, cause to be coated with
The thickness and surface density of pole piece fringe region cannot be effectively obtained control and guarantee.
Invention content
The technical problems to be solved by the invention are：For existing negative plate slurry coating there are edge Pian Bao regions
And battery is caused to there is technical issues that, provide a kind of negative plate and preparation method thereof and including the negative plate
Lithium ion battery.
In order to solve the above technical problems, an embodiment of the present invention provides a kind of negative plate, including negative current collector and attached
It in the negative electrode material layer on the negative current collector surface, the negative electrode material layer includes the first negative electrode material layer and the second cathode
Material layer；
First negative electrode material layer is attached to the surface of the negative current collector, and first negative electrode material layer includes the
One material sections and in the second material sections of the first material area edge, the thickness of first material sections are more than described the
The thickness of two material sections, second negative electrode material layer are attached to the surface of second material sections, second negative material
Layer is in the edge of first negative electrode material layer.
Optionally, second negative electrode material layer and the overall thickness of second material sections are less than or equal to first material
Expect the thickness in area, the unit area total capacities of second negative electrode material layer and second material sections is greater than or equal to described the
The capacity per unit area of one negative electrode material layer.
Optionally, first negative electrode material layer includes the first negative electrode active material, the first conductive agent and first adhesive,
Second negative electrode material layer includes the second negative electrode active material, the second conductive agent and second adhesive.
Optionally, the gram volume of second negative electrode active material is more than the gram volume of first negative electrode active material.
Optionally, first negative electrode active material be native graphite, it is Delanium, petroleum coke, hard carbon, soft carbon, organic
Crack carbon, carbonaceous mesophase spherules, elemental silicon, silicon-carbon compound, Si oxide, silicon alloy, elemental Germanium, simple substance tin, tin alloy, tin
It is one or more in oxide, transition metal oxide, niobium base oxide, lithium titanate and black phosphorus；
Second negative electrode active material for native graphite, Delanium, petroleum coke, hard carbon, soft carbon, organic cracking carbon,
Carbonaceous mesophase spherules, elemental silicon, silicon-carbon compound, Si oxide, silicon alloy, elemental Germanium, simple substance tin, tin alloy, tin-oxide,
It is one or more in transition metal oxide, niobium base oxide, lithium titanate, black phosphorus, carbon nanotube and graphene.
Optionally, first conductive agent and second conductive agent are independently selected from conductive carbon black, acetylene black, carbon
It is one or more in nanotube, electrically conductive graphite, carbon fiber and graphene；
The first adhesive and the second adhesive are independently selected from polyacrylic acid, polyacrylate, poly- third
Alkene lonitrile copolymer, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, butadiene-styrene rubber, polyimides, polyethylene glycol oxide, polyvinylpyrrolidine
It is one or more in ketone, sodium alginate, gelatin, sodium carboxymethylcellulose, guar gum, xanthans and chitosan.
Optionally, first negative electrode material layer includes following mass component：First 80-99 parts of negative electrode active material, the
1-10 parts of 0-10 parts of the matter of one conductive agent and first adhesive.
Optionally, second negative electrode material layer includes following mass component：Second 80-99 parts of negative electrode active material, the
1-10 parts of two 0-10 parts of conductive agents and second adhesive.
Another embodiment of the present invention provides a kind of preparation method of the negative plate, includes the following steps：
The slurry of first negative material is provided；
The slurry of second negative material is provided；
The surface that the slurry of first negative material is coated on to negative current collector forms the first negative electrode material layer, the first cathode
Material layer includes the first material sections and in the second material sections of the first material area edge, and the thickness of the first material sections is more than the
The thickness of two material sections, the surface that the slurry material of the second negative material is coated on to the second material sections form the second negative material
Layer, is then dried, and is formed negative electrode material layer, is obtained negative plate.
Another embodiment of the present invention also provides a kind of lithium ion battery, including battery case, is set to the battery case
Interior battery core and the electrolyte being filled in the battery case；
The battery core includes the positive plate, diaphragm and the negative plate that set gradually；The negative plate is above-mentioned negative plate.
The negative plate provided according to embodiments of the present invention forms second by being coated with the second negative material in the second material sections
Negative electrode material layer so that the unit area total capacity of the second negative electrode material layer and the second material sections increases, so as to reduce tradition
Negative plate easily generates the risk of battery short circuit caused by Li dendrite, reduces lithium ion battery because edge-coating amount is relatively low
The probability of happening of safety accident improves the security performance of lithium ion battery.
Description of the drawings
Fig. 1 is the schematic diagram that negative current collector is coated with the first negative electrode material layer in a certain embodiment of the present invention；
Fig. 2 is the schematic diagram of negative current collector coating negative electrode material layer in a certain embodiment of the present invention.
Reference numeral in specification is as follows：
1st, negative current collector；
2nd, negative electrode material layer；21st, the first negative electrode material layer；211st, the first material sections；212nd, the second material sections；22nd, second
Negative electrode material layer.
Specific embodiment
In order to which technical problem solved by the invention, technical solution and advantageous effect is more clearly understood, below in conjunction with
Accompanying drawings and embodiments, the present invention is further described in detail.It should be appreciated that specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
As shown in Fig. 1 and 2, the negative plate of one embodiment of the invention offer including negative current collector 1 and is attached to described
The negative electrode material layer 2 on 1 surface of negative current collector, the negative electrode material layer 2 include the first negative electrode material layer 21 and the second cathode material
The bed of material 22；
First negative electrode material layer 21 is attached to the surface of the negative current collector 1, first negative electrode material layer 21
Including the first material sections 211 and in second material sections 212 at 211 edge of the first material sections, first material sections
211 thickness is more than the thickness of second material sections 212, and second negative electrode material layer 22 is attached to second material sections
212 surface, second negative electrode material layer 22 are in the edge of first negative electrode material layer 21.
The second negative electrode material layer 22 is formed by being coated with the second negative material in the second material sections 212 so that the second material
The unit area total capacity of 212 and second negative electrode material layer 22 of area increases, so as to reduce traditional negative plate because of edge-coating amount
It is relatively low, the risk of battery short circuit caused by Li dendrite is easily generated, reduces the probability of happening of lithium ion battery safety accident,
Improve the security performance of lithium ion battery.
It should be understood that when being coated with the first negative material the first negative electrode material layer 21 of formation on negative current collector 1, can not keep away
The meeting exempted from generates the situation of thick middle thin edge, i.e. the first negative electrode material layer 21 forms the first material sections 211 and in institute
Second material sections 212 at 211 edge of the first material sections are stated, the thickness of the second material sections 212 is too thin, leads to the second material sections 212
Capacity it is relatively low or even the capacity of the positive plate of its corresponding position can be less than, therefore there are the risk of Li dendrite, it is therefore desirable to
One layer of second negative electrode material layer 22 is coated on the second material sections 212, to improve the capacity of the second material sections of negative plate 212,
To reduce the risk of Li dendrite.
In a certain embodiment, the type of above-mentioned negative current collector 1 is known to those skilled in the art, preferably has
Negative current collector 1 made of the material of good electrochemical stability, electric conductivity and mechanical strength, for example, negative current collector 1 can
Think copper foil, copper has high conductivity.
In a certain embodiment, the overall thickness of second negative electrode material layer 22 and second material sections 212 be less than or
Equal to the thickness of first material sections 211, second negative electrode material layer 22 and the unit area of second material sections 212
Total capacity is greater than or equal to the capacity per unit area of first negative electrode material layer 21.
The second negative electrode material layer 22 is formed by being coated with the second negative material in the second material sections 212, controls the second cathode
The overall thickness of 22 and second material sections 212 of material layer is less than or equal to the thickness of the first material sections 211, the second negative electrode material layer 22
It is greater than or equal to the capacity per unit area of the first material sections 211 with the unit area total capacity of the second material sections 212, so as to improve
The total capacity of second negative electrode material layer 22 and the second material sections 212, ensure that the second negative electrode material layer 22 and the second material sections
212 total capacity is greater than or equal to the capacity of the first material sections 211, it is ensured that the second negative electrode material layer 22 on negative plate and the
The total capacity of two material sections 212 is not less than design value, so as to avoid because generated during negative plate off-capacity Li dendrite so as to
Caused battery short circuit problem reduces the probability of happening of lithium ion battery safety accident, improves the safety of lithium ion battery
Performance.
Meanwhile by the second material sections 212 be coated with the second negative material formed the second negative electrode material layer 22, eliminate by
The problem of capacity per unit area that second material sections 212 are brought is relatively low, it is therefore not necessary to deliberately go the characteristic by adjusting slurry with
And the means such as painting parameter of coating die head of adjustment coating machine generate the phenomenon that partially thin to reduce on negative plate.Even if negative plate
In the presence of it is partially thin the phenomenon that, can also can be efficiently controlled negative by being coated with the second negative electrode material layer 22 on the second material sections 212
The thickness and surface density of second material sections 212 of pole piece.
In a certain embodiment, first negative electrode material layer 21 include the first negative electrode active material, the first conductive agent and
First adhesive, second negative electrode material layer 22 include the second negative electrode active material, the second conductive agent and second adhesive.
In a certain embodiment, the gram volume of second negative electrode active material is more than first negative electrode active material
Gram volume.It is more than the material of the gram volume of the first negative electrode active material by using the gram volume of the second negative electrode active material, is
Reach the capacity per unit area identical with the first material sections 211, it is possible to reduce the coating weight of the second negative material, so that the
The overall thickness of two material sections 212 and the second negative electrode material layer 22 is not more than the thickness of the first material sections 211.Due to the second material sections
212 and second negative electrode material layer 22 overall thickness reduction, avoid negative plate edge generate drum side the phenomenon that, so as to improve
The production qualification rate of negative plate.
When the gram volume of second negative electrode active material is equal to the gram volume of the first negative electrode active material, it is ensured that the second cathode
The capacity of 22 and second material sections 212 of material layer is not less than the capacity of the first material sections 211, then the second negative electrode material layer 22 and the
The overall thickness of two material sections 212 need to be greater than or equal to the thickness of the first material sections 211；Moreover, in process of production, negative plate
When controlling of production process is bad, the overall thickness for being easy to cause the second negative electrode material layer 22 and the second material sections 212 is more than the first material
Expect the thickness in area 211, since the out-of-flatness of negative plate is so as to cause the edge of negative plate the phenomenon that drum side occur, lead to negative plate
Scrappage improve.When the gram volume of second negative electrode active material is less than the gram volume of the first negative electrode active material, it is ensured that the
The total capacity of two negative electrode material layers 22 and the second material sections 212 is not less than the capacity of the first material sections 211, needs increase by second negative
The coating weight of pole material layer 22, the overall thickness for being easy to cause the second negative electrode material layer 22 and the second material sections 212 are more than the first material
Expect the thickness in area 211, this necessarily causes the edge of negative plate to generate the phenomenon that rousing side, and negative plate scrappage is caused to improve.
First negative electrode active material and the second negative electrode active material are not particularly limited, as long as can be embedded in and
Release the active material of lithium ion.For example, first negative electrode active material is native graphite, Delanium, oil
Coke, hard carbon, soft carbon, organic cracking carbon, carbonaceous mesophase spherules, elemental silicon, Si oxide, silicon alloy, silicon-carbon compound, simple substance
Germanium, simple substance tin, tin alloy, tin-oxide, transition metal oxide, niobium base oxide, lithium titanate and one kind or more in black phosphorus
Kind.In order to obtain battery more preferably chemical property, the first negative electrode active material preferred natural graphite or Delanium.
In a certain embodiment, second negative electrode active material is native graphite, Delanium, petroleum coke, hard carbon, soft
Carbon, organic cracking carbon, carbonaceous mesophase spherules, elemental silicon, Si oxide, silicon alloy, silicon-carbon compound, elemental Germanium, simple substance tin, tin
One kind in alloy, tin-oxide, transition metal oxide, niobium base oxide, lithium titanate, black phosphorus, carbon nanotube and graphene
It is or a variety of.It should be understood that it is higher than the gram volume of the first negative electrode active material in the gram volume for ensureing the second negative electrode active material
Under the premise of, the first negative electrode active material can be identical with the second negative electrode active material, can not also be identical.
The present invention is not particularly limited the first conductive agent and the second conductive agent, for example, first conductive agent and institute
The second conductive agent is stated to be independently selected from conductive carbon black, acetylene black, carbon nanotube, electrically conductive graphite, carbon fiber and graphene
It is one or more.
Adhesive is not particularly limited in the present invention, if can ensure that the first negative material and negative current collector 1 it
Between bond and be not easily stripped, bond and be not easily stripped between the second negative material and the first negative material or negative current collector 1.Example
Such as, it is common to be independently selected from polyacrylic acid, polyacrylate, polyacrylonitrile for the first adhesive and the second adhesive
Polymers, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, butadiene-styrene rubber, polyimides, polyethylene glycol oxide, polyvinylpyrrolidone, seaweed
It is one or more in sour sodium, gelatin, sodium carboxymethylcellulose, guar gum, xanthans and chitosan.
In a certain embodiment, the first adhesive or the second adhesive can also form glue with cathode solvent
Object, the cathode solvent are selected from water, acetone, N monomethyls pyrrolidones, tetrahydrofuran, dimethyl sulfoxide (DMSO), methyl ethyl ketone or acetic acid second
One or more of ester.
In order to improve the capacity and electric conductivity of the first negative material and the second negative material, meanwhile, the first negative material with
Better cementability is obtained between second negative material and negative current collector 1, better ability of aggregation is obtained between particle, it is described
First negative electrode material layer 21 includes following mass component：First 80-99 parts of negative electrode active material, 0-10 parts of the matter of conductive agent and institute
State 1-10 parts of adhesive.Wherein, the first conductive agent is preferably 1-10 parts, it is preferable that first negative electrode material layer 21 is by following
Mass fraction forms：1-10 parts of first 80-98 parts of negative electrode active material, 1-10 parts of the matter of the first conductive agent and first adhesive.
Second negative electrode material layer 22 includes following mass component：Second 80-99 parts of negative electrode active material, the second 0-10 parts of conductive agent
With 1-10 parts of second adhesive.Wherein, the second conductive agent is preferably 1-10 parts, it is preferable that second negative electrode material layer 22 by
Following mass fraction composition：1-10 parts of second 80-98 parts of negative electrode active material, 1-10 parts of conductive agent and adhesive.
Meanwhile the present invention also provides the preparation method of above-mentioned negative plate, include the following steps：
The slurry of first negative material is provided；
The slurry of second negative material is provided；
By the slurry of the first negative material be coated on negative current collector 1 surface formed the first negative electrode material layer 21, first
Negative electrode material layer 21 includes the first material sections 211 and the second material sections 212 in 211 edge of the first material sections, the first material
Expect that the thickness in area 211 is more than the thickness of the second material sections 212, the slurry material of the second cathode material is coated on the second material sections 212
Surface formed the second negative electrode material layer 22, then dry, formed negative electrode material layer 2, obtain negative plate.
According to the present invention, first, the slurry of the first negative material is provided, the slurry of the first negative material can select outsourcing
Or it can be prepared by existing method, such as by the first negative electrode active material, the first conductive agent, first adhesive and negative
Pole solvent is made after mixing according to a certain percentage.Above-mentioned first negative electrode active material, the first conductive agent and first adhesive
Used substance and respective additive amount are as it was noted above, details are not described herein.
Then, the slurry of the second negative material is provided, the slurry of the second negative material can select outsourcing or can be by existing
Some methods are prepared, for example, by the second negative electrode active material, the second conductive agent, second adhesive and cathode solvent according to
Certain proportion is made after mixing.Object used by above-mentioned second negative electrode active material, the second conductive agent and second adhesive
Matter and respective additive amount are as it was noted above, details are not described herein.
The gram volume of second negative electrode active material of above-mentioned selection is more than the gram volume of the first negative electrode active material.
Cathode solvent is used for the first negative electrode active material, the second negative electrode active material, the first conductive agent, the first bonding
Agent, the second conductive agent and second adhesive are distributed in wherein, pulp-like are formed, conducive to coating.It is above-mentioned in follow-up drying process
Cathode solvent is removed.Specific substance and additive amount are known to a person skilled in the art used by cathode solvent,
This is repeated no more.
Finally, the surface for the first negative material being coated on to negative current collector 1 forms the first negative electrode material layer 21, and first is negative
Pole material layer 21 includes the first material sections 211 and the second material sections 212 in 211 edge of the first material sections, the first material
The thickness in area 211 is more than the thickness of the second material sections 212, and the second negative material is coated on to the surface shape of the second material sections 212
It into the second negative electrode material layer 22, then dries, forms negative electrode material layer 2, obtain negative plate.
Specifically, negative current collector 1 of the prior art may be used in negative current collector 1, then by the first negative material
Slurry by coating machine be coated on negative current collector 1 upper and lower surface formed the first negative electrode material layer 21, at this point, the first cathode
There is thick middle and thin edge in material layer 21, therefore, the first negative electrode material layer 21 forms the first material sections 211 and packet
Enclose the second material sections 212 of the first material sections 211；The slurry of the second negative material is coated on the second material by coating machine again
The surface in area 212 forms the second negative electrode material layer 22, controls the second negative electrode material layer 22 and the overall thickness of the second material sections 212 small
In or equal to the first negative electrode material layer 21 thickness；Then it is dried, then is obtained after carrying out roll-in and cutting at a certain temperature
To negative plate.
In the present invention, existing extrusion coater can be used to realize in the first negative material of coating, is coated with the second cathode
The coating machine of Xu Hesheng scientific ＆ technical corporation of Shenzhen offer can be used to realize in material.
In the present invention, the agitating mode for preparing and being used during the first negative material and the second negative material is not limited, it can
Agitating mode well known in the art to be used to be stirred, for example, can be stirred in a manner of dry-mixed, can also pass through
The mode of wet mixing is stirred.
The concrete technology and method of the coating of above-mentioned slurry are known in the art, are repeated no more in the present invention.
In addition, the present invention also provides a kind of lithium ion battery, including battery case, it is set in the battery case
Battery core and the electrolyte being filled in the battery case；
The battery core includes the positive plate, diaphragm and the negative plate that set gradually；The negative plate is foregoing cathode
Piece.
In lithium ion battery disclosed by the invention, negative plate is prepared for method disclosed by the invention, and positive plate can lead to
Existing method is crossed to be prepared.
For above-mentioned lithium ion battery, there is no limit may be used this for battery case, electrolyte, positive plate and diaphragm
The existing technical need in field is selected.
Lithium ion battery may be used existing method and be prepared, for example, by above-mentioned positive plate, diaphragm and negative plate according to
It is secondary to be overlapped into battery core, it is fitted into battery case, injects the electrolyte into battery case, through sealing, being melted into, partial volume and standing makes
Into lithium ion battery.
The present invention is further detailed by the following examples.
Embodiment 1
1. the preparation of negative plate
It is prepared by the slurry of 1.1 first negative materials.
CMC (sodium carboxymethylcellulose) is first prepared into aqueous solution；
Conductive carbon black is added in CMC aqueous solutions to be mixed, and then adds in Delanium (Shenzhen Bei Teruixin
Energy and material limited company produces, gram volume 360mAH/g) continue to stir；
SBR (butadiene-styrene rubber) lotion is added, continues to be mixed evenly.Wherein Delanium:Conductive carbon black:CMC:
The weight ratio of SBR is 96:1:1.5:1.5.
It is prepared by the slurry of 1.2 second negative materials.
CMC is first prepared into aqueous solution；
Conductive carbon black is added in CMC aqueous solutions to be mixed, and is then added in the sub- Si-C composite material of oxidation and (is purchased from
Shenzhen City Beiterui New Energy Materials Co., Ltd, gram volume 380mAH/g) continue to stir；
SBR emulsion is added, continues to be mixed evenly.Wherein aoxidize sub- Si-C composite material：Conductive carbon black:CMC:
The weight ratio of SBR is 94.5:1:1.5:3.
The coating of 1.3 negative plates
The slurry of first negative material is uniformly coated to form first in the upper and lower surface for the copper foil that thickness is 10 μm
Negative electrode material layer, the first negative electrode material layer include the first material sections and in the second material sections of the first material area edge, the
The thickness of one material sections and the thickness of the second material sections are shown in Table 1, then the slurry of the second negative material is coated on the second material sections
Surface form the second negative electrode material layer, then toast drying at 80 DEG C, then negative plate is obtained after roll-in, cutting.
2. the preparation of positive plate
It is prepared by the slurry of 2.1 positive electrodes
By nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2), conductive black (purchased from Switzerland Te Migao, the trade mark is super P)
It is dispersed in N-Methyl pyrrolidone with Kynoar (being purchased from Kynar, trade mark HSV900), forms anode sizing agent.Wherein,
Nickle cobalt lithium manganate:Conductive black:The weight ratio of Kynoar is 97:2:1, the solid content of anode sizing agent obtained is 70%.
The coating of 2.2 positive plates
Anode sizing agent is uniformly coated to form positive electrode material layer on the upper and lower surface for the aluminium foil that thickness is 16 μm, then
It is 5 minutes dry at 100 DEG C, then obtain positive plate after roll-in, cutting.
3. the preparation of lithium ion battery
Respectively by above-mentioned positive plate, negative plate and polypropylene diaphragm by being wound into a rectangular lithium ion battery pole
Core, then be inserted in shell with square aluminum, after baking, by the suitable injection shell with square aluminum of electrolyte, sealing using ageing, is melted into
And lithium ion battery is made after the processes such as partial volume.Wherein, electrolyte LiPF6The EC (ethylene carbonate) of (lithium hexafluoro phosphate)/
EMC (methyl ethyl carbonate)/DEC (diethyl carbonate)/VC (ethylene carbonate) mixed solution, LiPF6A concentration of 1mol/L, VC
2%, the EC for entire electrolyte weight:EMC:The volume ratio of DEC is 1:1:1.
Embodiment 2
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：First negative material
Slurry in Delanium:CMC:The weight ratio of SBR is 98:1:1.
Embodiment 3
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：First negative material
Slurry in using native graphite replace Delanium, native graphite:Conductive carbon black:CMC:The weight ratio of SBR is 96:1:1:2.
Wherein, the gram volume of native graphite is 360mAh/g.
Embodiment 4
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：Second negative material
Slurry in the oxidation Asia Si-C composite material that uses, gram volume 420mAh/g.
Embodiment 5
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：Second negative material
Slurry in silicon-carbon-Delanium composite material be compounded to form using Si-C composite material and Delanium replace the sub- silicon-carbon of oxidation
The gram volume of composite material, wherein Si-C composite material is 500mAh/g, and the gram volume of Delanium is 355mAg/g, according to silicon
Carbon composite is 3 with Delanium weight ratio:7 carry out being compounded to form composite mortar, and the gram volume of composite mortar is
398.5mAh/g。
Embodiment 6
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：Second negative material
Slurry in the oxidation Asia Si-C composite material that uses, gram volume 420mAh/g aoxidizes sub- Si-C composite material:Conductive carbon
It is black:CMC:The weight ratio of SBR is 94:1:1.5:3.5.
Embodiment 7
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：Second negative material
Slurry in the oxidation Asia Si-C composite material that uses, gram volume 420mAh/g replaces conductive black using carbon nanotube
With PAA (polyacrylic acid) instead of SBR, sub- Si-C composite material is aoxidized:Carbon nanotube:CMC:The weight ratio of PAA is 93:1:1:5.
Embodiment 8
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：Second negative material
Slurry in silicon-carbon-Delanium composite material be compounded to form using Si-C composite material and Delanium replace the sub- silicon-carbon of oxidation
Composite material and PAA (polyacrylic acid) increase carbon nanotube instead of SBR, and the gram volume of wherein Si-C composite material is
1000mAh/g, the gram volume of Delanium is 350mAh/g, is 5 according to the weight ratio of Si-C composite material and Delanium:5
Be compounded to form composite mortar, the gram volume of composite mortar is 675mAh/g, silicon-carbon-Delanium composite material:Carbon nanometer
Pipe:Conductive carbon black:CMC:The weight ratio of PAA is 80:2:6:2:10.
Embodiment 9
Method according to embodiment 1 prepares negative plate, positive plate and lithium ion battery, difference lies in：First negative material
Slurry in the gram volume of Delanium that uses for 330mAh/g, Delanium that the slurry of the second negative material uses,
Gram volume is 355mAh/g.
Negative plate tests its surface density respectively made from embodiment 1-9, then utilizes the calculation formula of capacity per unit area
The capacity per unit area of negative plate is calculated, test result is shown in Table 1.The calculation formula of capacity per unit area is：Capacity per unit area
The weight ratio of the gram volume * active materials of=surface density * active materials.
The test method of surface density：The area of negative plate is denoted as S, and weighs its total weight as M, according to copper foil in negative plate
Surface density calculate the weight of copper foil in negative plate as m, then the surface density of the negative plate of unit area=(M-m)/S.
Table 1
In above-mentioned table 1, the thickness of the second material sections is region value therebetween, the second negative electrode material layer and the second material
The overall thickness in area is region value therebetween；The unit of thickness is μm that the unit of capacity per unit area is mAh/ (cm*
cm)。
By in table 1 it is found that negative plate inevitably will appear the second material when the first negative electrode material layer is coated with
Expect area, and the capacity per unit area of the second material sections is significantly lower than the capacity per unit area of the first material sections.Lithium ion battery exists
During design, the capacity per unit area of the ratio positive plate of the capacity per unit area design of negative plate is big, but is built upon negative plate
The coating of the first negative material it is uniform in the case of, because of the coating of the first negative material, there are the second material sections, lead to its unit
Area capacity declines, and the capacity per unit area of positive plate is corresponded to so as to be less than it there are the capacity per unit area of the second material sections
Situation so that the capacity per unit area of negative plate is less than the capacity per unit area of positive plate, and lithium ion battery is caused to generate lithium branch
It is brilliant.
By in table 1 it is found that by increasing the second negative electrode material layer, the second material sections and the second cathode in the second material sections
The unit area total capacity of material layer significantly improves or even can be higher than the capacity per unit area of the first material sections.Because on negative plate
Capacity per unit area increase, so as to reduce traditional negative plate because edge-coating amount is relatively low, easily generate Li dendrite and lead
The risk of the battery short circuit of cause reduces the probability of happening of lithium ion battery safety accident, improves the safety of lithium ion battery
Performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of negative plate, which is characterized in that including negative current collector and be attached to the cathode on the negative current collector surface
Material layer, the negative electrode material layer include the first negative electrode material layer and the second negative electrode material layer；
First negative electrode material layer is attached to the surface of the negative current collector, and first negative electrode material layer includes the first material
Expect area and in the second material sections of the first material area edge, the thickness of first material sections is more than second material
Expect the thickness in area, second negative electrode material layer is attached to the surface of second material sections, at second negative electrode material layer
In the edge of first negative electrode material layer.
2. negative plate according to claim 1, which is characterized in that second negative electrode material layer and second material sections
Overall thickness be less than or equal to the thickness of first material sections, the list of second negative electrode material layer and second material sections
Plane product total capacity is greater than or equal to the capacity per unit area of first negative electrode material layer.
3. negative plate according to claim 1, which is characterized in that first negative electrode material layer includes the first negative electrode active
Material, the first conductive agent and first adhesive, second negative electrode material layer include the second negative electrode active material, the second conductive agent
And second adhesive.
4. negative plate according to claim 3, which is characterized in that the gram volume of second negative electrode active material is more than institute
State the gram volume of the first negative electrode active material.
5. negative plate according to claim 3, which is characterized in that first negative electrode active material is native graphite, people
Make graphite, petroleum coke, hard carbon, soft carbon, organic cracking carbon, carbonaceous mesophase spherules, elemental silicon, silicon-carbon compound, Si oxide, silicon
In alloy, elemental Germanium, simple substance tin, tin alloy, tin-oxide, transition metal oxide, niobium base oxide, lithium titanate and black phosphorus
It is one or more；
Second negative electrode active material is native graphite, Delanium, petroleum coke, hard carbon, soft carbon, organic cracking carbon, centre
Phase carbosphere, elemental silicon, silicon-carbon compound, Si oxide, silicon alloy, elemental Germanium, simple substance tin, tin alloy, tin-oxide, transition
It is one or more in metal oxide, niobium base oxide, lithium titanate, black phosphorus, carbon nanotube and graphene.
6. negative plate according to claim 3, which is characterized in that first conductive agent and second conductive agent are mutual
It is one or more in conductive carbon black, acetylene black, carbon nanotube, electrically conductive graphite, carbon fiber and graphene；
The first adhesive and the second adhesive are independently selected from polyacrylic acid, polyacrylate, polyacrylonitrile
Copolymer, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, butadiene-styrene rubber, polyimides, polyethylene glycol oxide, polyvinylpyrrolidone, sea
It is one or more in mosanom, gelatin, sodium carboxymethylcellulose, guar gum, xanthans and chitosan.
7. negative plate according to claim 3, which is characterized in that first negative electrode material layer includes following quality group
Point：1-10 parts of first 80-99 parts of negative electrode active material, 0-10 parts of the matter of the first conductive agent and first adhesive.
8. negative plate according to claim 3, which is characterized in that second negative electrode material layer includes following quality group
Point：1-10 parts of second 80-99 parts of negative electrode active material, the second 0-10 parts of conductive agent and second adhesive.
9. the preparation method of negative plate according to any one of claims 1 to 8, which is characterized in that include the following steps：
The slurry of first negative material is provided；
The slurry of second negative material is provided；
The surface that the slurry of first negative material is coated on to negative current collector forms the first negative electrode material layer, the first negative material
Layer includes the first material sections and in the second material sections of the first material area edge, and the thickness of the first material sections is more than the second material
Expect the thickness in area, the surface that the slurry material of the second cathode material is coated on to the second material sections forms the second negative electrode material layer, then
It is dry, negative electrode material layer is formed, obtains negative plate.
10. a kind of lithium ion battery, which is characterized in that including battery case, the battery core being set in the battery case and
The electrolyte being filled in the battery case；
The battery core includes the positive plate, diaphragm and the negative plate that set gradually；The negative plate is claim 1-8 any one
The negative plate.
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