CN109994710A - Composite negative electrode material, preparation method thereof, negative electrode plate and battery - Google Patents
Composite negative electrode material, preparation method thereof, negative electrode plate and battery Download PDFInfo
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- CN109994710A CN109994710A CN201711478105.8A CN201711478105A CN109994710A CN 109994710 A CN109994710 A CN 109994710A CN 201711478105 A CN201711478105 A CN 201711478105A CN 109994710 A CN109994710 A CN 109994710A
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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
- H01M4/36—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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- Y02E60/10—Energy storage using batteries
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Abstract
The application provides a composite negative electrode material and a preparation method thereof, a negative electrode pole piece and a battery, wherein the composite negative electrode material comprises a negative electrode material center core and a coating layer coated on the surface of the negative electrode material center core, and the coating layer comprises an inorganic polymer or an organic derivative of the inorganic polymer. The negative electrode material can effectively inhibit the volume expansion of the negative electrode material in the charging and discharging process, inhibit the rebound of the negative electrode pole piece, and improve the electrochemical performance of the battery.
Description
Technical field
This application involves field of batteries, and in particular to a kind of composite negative pole material and preparation method thereof, cathode pole piece, electricity
Pond.
Background technique
Lithium ion secondary battery have high capacity, long circulating, memory-less effect, self discharge is few, use temperature range is wide, high
The advantages that multiplying power, is widely applied to the fields such as mobile phone, computer, electric bicycle and electric car.Lithium ion secondary battery
In use, since the insertion of lithium ion is deviate from, volume expansion can occur for positive and negative anodes pole piece, affect lithium ion secondary electricity
The performance in pond.Silicon based anode material has many advantages, such as high capacity, good cycle and good rate capability, increasingly by research and development people
The attention of member, but its volume expansion in charge and discharge process is larger, seriously affects the use of lithium ion secondary battery, answers it
With being restricted.
In consideration of it, special propose the application.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of composite negative pole material and its preparation
Method, cathode pole piece, battery, effectively volume expansion of the inhibition negative electrode material in charge and discharge process, inhibit cathode pole piece anti-
Bullet improves the chemical property of battery.
In order to achieve the above object, the application's in a first aspect, being wrapped this application provides a kind of composite negative pole material
It includes negative electrode material centronucleus and is coated on the clad on negative electrode material centronucleus surface, the clad includes inorganic polymer
Or the organic derivative of inorganic polymer.
In the second aspect of the application, this application provides a kind of preparation method of composite negative pole material, it is used to prepare this
Apply for composite negative pole material described in first aspect, comprising steps of negative electrode material, optional conductive agent are added to polymerizable type
In small-molecule substance solution, curing agent is added thereto under agitation and carries out polymerization reaction, drying removes after reaction
Solvent to get arrive composite negative pole material.
In the third aspect of the application, this application provides a kind of cathode pole pieces comprising negative current collector and cathode
Active material layer, negative electrode active material layer are located on the surface of negative current collector, and the negative electrode active material layer includes according to this
Apply for composite negative pole material described in first aspect.
In the fourth aspect of the application, this application provides a kind of batteries comprising according to the application third aspect
Cathode pole piece.
Compared with the existing technology, the application include at least it is as described below the utility model has the advantages that
The application forms one layer of inorganic polymer clad or inorganic polymer in the in situ Polymerization of negative electrode material
Organic derivative clad can significantly improve the cementability of negative electrode material, effectively inhibit negative electrode material in charge and discharge process
In volume expansion, inhibit cathode pole piece rebound, improve the chemical property of battery.
Specific embodiment
The following detailed description of composite negative pole material according to the application and preparation method thereof, cathode pole piece, battery.
Illustrate the composite negative pole material according to the application first aspect first comprising negative electrode material centronucleus and cladding
Clad on negative electrode material centronucleus surface, the clad include organic derivative of inorganic polymer or inorganic polymer
Object.
In the composite negative pole material of the application first aspect, the inorganic polymer be selected from silicate inorganic polymer,
One or more of phosphate inorganic polymer, aluminosilicate inorganic polymer.The organic derivative of the inorganic polymer
Refer to and introduces the organic group containing carbon atom in the structure of inorganic polymer.
In the composite negative pole material of the application first aspect, in the composite negative pole material, the clad contains
Amount is unsuitable excessively high, and the capacity that otherwise will affect negative electrode material plays.Specifically, in the composite negative pole material, the cladding
The mass content of layer is less than or equal to 40%, it is preferable that the mass content of the clad is less than or equal to 20%.
In the composite negative pole material of the application first aspect, the negative electrode material centronucleus can be selected from silicon-based anode material
One or more of material, tin base cathode material.Preferably, it is compound to be selected from silicon, Si oxide, silicon-carbon for the silicon based anode material
One or more of object, silicon alloy.Silicon can be selected from nano silicon particles, silicon nanowires, nano-tube, silicon thin film, 3D porous silicon,
One or more of hollow porous silicon.The tin base cathode material is selected from one of tin, tin-oxide, tin alloy or several
Kind.
In the composite negative pole material of the application first aspect, the negative electrode material can carry out surface hydroxylation processing, with
Convenient for the cladding of clad.
In the composite negative pole material of the application first aspect, conductive agent can be also contained in the clad, conductive agent can
Further to improve negative electrode material, such as the electric conductivity of silicon based anode material, tin base cathode material, can also avoid in negative electrode material
Surface, which forms excessively fine and close clad, influences the transmission of electronics.
In the composite negative pole material of the application first aspect, clad is by polymerizable type small-molecule substance in cathode material
The in situ Polymerization of material is formed.When polymerization process of the polymerizable type small-molecule substance on negative electrode material surface is in-situ polymerization,
The organic derivative and negative electrode material that inorganic polymer or inorganic polymer in clad can be achieved fit closely, and have
The characteristics of intensity is big, good toughness, can tolerate expansion and receipts of the negative electrode material during embedding lithium ionic insertion/deinsertion (or other ions)
Contracting guarantees the high resiliency and toughness of the SEI film on negative electrode material surface, and the lithium ion (or other ions) reduced in cyclic process disappears
Consumption, the significant service life for extending battery.Particularly, the application is particularly suitable for the charge and discharges such as silicon based anode material, tin base cathode material
Negative electrode material with larger volume expansion in electric process, both can be effectively suppressed silicon based anode material, tin base cathode material etc. and had existed
Volume expansion in charge and discharge process inhibits cathode pole piece rebound, moreover it is possible to help to obtain high capacity, good cycle and multiplying power
The good battery of performance.Preferably, the polymerizable type small-molecule substance is selected from inorganic silicate, inorganic phosphate, inorganic aluminic acid
One or more of salt, ethyl orthosilicate, kaolin.Wherein, inorganic silicate, inorganic phosphate, in inorganic aluminate
The type of cationic portion is unrestricted, preferably alkali metal, alkaline-earth metal, further preferably alkali metal, further excellent
It is selected as sodium or potassium.Inorganic phosphate can be orthophosphates, dihydric phosphate, phosphoric acid sesquialter hydrogen salt or hydrophosphate again.Further
Preferably, inorganic silicate can be waterglass.
By taking waterglass as an example, polymerization process are as follows:
Waterglass can gradually hydrolyze generation [Si (OH) under curing agent promotion in aqueous solution4] unimolecule, this single point
Son is polymerize with different rates, and gradually form monomeric form has larger active Si (OH)4It is lower with the degree of polymerization
Silicate polymer, then with the hydroxy combining on negative electrode material surface, first negative electrode material surface formed epipole, gradually form with
Amorphous Si O2·nH2Clad existing for O form, reaction process are as follows:
Secondly explanation is according to the preparation method of the composite negative pole material of the application second aspect, is used to prepare the application the
Composite negative pole material described in one side, comprising steps of negative electrode material, optional conductive agent are added to polymerizable type small molecule
In substance solution, curing agent is added thereto under agitation and carries out polymerization reaction, drying removes solvent after reaction, i.e.,
Obtain composite negative pole material.
In the preparation method of the composite negative pole material of the application second aspect, the polymerizable type small-molecule substance is selected from
One or more of inorganic silicate, inorganic phosphate, inorganic aluminate, ethyl orthosilicate.Wherein, inorganic silicate, nothing
The type of cationic portion in machine phosphate, inorganic aluminate is unrestricted, preferably alkali metal, alkaline-earth metal, further
Preferably alkali metal is still more preferably sodium or potassium.Inorganic phosphate can be again orthophosphates, dihydric phosphate, phosphoric acid times
Half hydrogen salt or hydrophosphate.
In the preparation method of the composite negative pole material of the application second aspect, the type of the curing agent is unrestricted,
It can be selected according to demand.The curing agent can be inorganic matter, such as metal oxide, hydroxide, metal salt, the solidification
Agent can also be organic matter, such as silane coupling agent, ethyl acetate.Specifically, the curing agent can be selected from magnesia, calcium oxide, oxygen
Change aluminium, copper oxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, aluminium chloride, salt
One or more of acid, dilute sulfuric acid, nitric acid, acetic acid, citric acid, silane coupling agent, ethyl acetate.
In the preparation method of the composite negative pole material of the application second aspect, make in polymerizable type small-molecule substance solution
The type of solvent is unrestricted, can be selected according to demand, can be used for example deionized water, organic solvent or go from
The mixed solution of sub- water and organic solvent.Wherein it is preferred to which organic solvent can be selected from ethyl alcohol, propylene glycol, N- crassitude
One or more of ketone, ethyl acetate.
In the preparation method of the composite negative pole material of the application second aspect, it is preferred that the mass fraction of active material
It is 70%~95%, the mass fraction of conductive agent is 0%~10%, the mass fraction of polymerizable type small-molecule substance is 3%~
25%, the mass fraction of curing agent is 1%~15%.The ratio of polymerizable type small-molecule substance is small, is unfavorable for being formed complete equal
The clad of even densification；The ratio of curing agent is small, and system possibly can not effectively solidify, and is unfavorable for forming the packet of complete even compact
Coating.
Illustrate the cathode pole piece according to the application third aspect again comprising negative current collector and negative electrode active material
Layer, negative electrode active material layer are located on the surface of negative current collector, and the negative electrode active material layer includes according to the application first
Composite negative pole material described in aspect.
In the cathode pole piece of the application third aspect, in the negative electrode active material layer, the application can be used only
Negative electrode active material of the composite negative pole material described in first aspect as cathode pole piece, can also be by the application first aspect institute
The composite negative pole material stated is used in mixed way with other common negative electrode materials.Preferably, the negative electrode active material layer can also wrap
Include other common negative electrode materials, for example, soft carbon, hard carbon, artificial graphite, natural graphite, carbonaceous mesophase spherules, lithium titanate, can be with
One or more of the metal of lithium formation alloy.
In the cathode pole piece of the application third aspect, the negative electrode active material layer may also include conductive agent and bonding
Agent.The type of conductive agent and binder is unrestricted, can be selected according to demand.
In the cathode pole piece of the application third aspect, the preparation method of cathode pole piece may include step: by negative electrode material,
Optional conductive agent is added in polymerizable type small-molecule substance solvent solution, be added thereto under agitation curing agent into
Row polymerization reaction, adds other common negative electrode materials, binder and conductive agent after lasting stirring a period of time, stirring is equal
Negative electrode slurry is obtained after even；Negative electrode slurry is coated on negative current collector, cathode pole piece is obtained after drying.It is polymerizable in this way
When type small-molecule substance in-situ solidifying, the cohesive strength of negative electrode active material layer can not only be enhanced, but also cathode can be promoted
Cohesive force between active material layer and negative current collector.
The battery according to the application fourth aspect will be illustrated next comprising anode pole piece, cathode pole piece, isolation film and
Electrolyte etc., wherein the cathode pole piece is cathode pole piece described in the application third aspect.
It can be secondary for lithium ion secondary battery, sodium ion secondary battery, zinc ion according to the battery of the application fourth aspect
Battery or magnesium ion secondary cell.It is only described in detail by taking lithium ion secondary battery as an example in this application, but the application is not
It is limited to this.
In a lithium ion secondary battery, positive active material can be selected from lithium-transition metal composite oxide, include lithium transition
Metal oxide (such as lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium
Nickel cobalt aluminum oxide), these lithium transition-metal oxides add in the compound that other transition metal or nontransition metal obtain
One or more of objects.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Comparative example 1
(1) preparation of cathode pole piece
Negative electrode active material, conductive agent and binder are thoroughly mixed in deionized water solvent system uniformly
Afterwards, it is coated on Cu foil, drying, cold pressing obtain cathode pole piece.Wherein negative electrode active material is artificial graphite and the sub- silicon of oxidation
(SiO) mixture, conductive agent are acetylene black, and binder is polyacrylic acid, and artificial graphite aoxidizes sub- silicon, acetylene black, polypropylene
The mass ratio of acid is 76:20:2:2.
(2) preparation of anode pole piece
By positive active material LiNi0.8Mn0.1Co0.1O2, conductive agent acetylene black, binder polyvinylidene fluoride press quality
After being thoroughly mixed in N-Methyl pyrrolidone dicyandiamide solution than 94:3:3 uniformly, it is coated on Al foil, it is drying, cold
Pressure, obtains anode pole piece.
(3) preparation of isolation film
Using PE porous polymer film as isolation film.
(4) preparation of electrolyte
In the in the mixed solvent of ethylene carbonate and methyl ethyl carbonate that mass ratio is 30:70, lithium salts LiPF is added6, mix
It closes uniformly, obtains electrolyte, wherein LiPF in electrolyte6Concentration be 1mol/L.
(5) preparation of lithium ion secondary battery
Anode pole piece, isolation film, cathode pole piece are folded in order, make isolation film be among positive and negative anodes pole piece play every
From effect, and wind obtain naked battery core.Naked battery core is placed in outer packing, the electrolyte prepared and encapsulation are injected.
Comparative example 2
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that the preparation of cathode pole piece
Used in aoxidize sub- silicon be the oxidation Asia silicon for having coated one layer of amorphous carbon.
Embodiment 1
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
70 mass parts are aoxidized into sub- silicon, (mass fraction is for 1 mass parts acetylene black and 25 mass parts sodium silicate aqueous solutions
20%, " 25 mass parts " indicate that sodium metasilicate is 25 mass parts in sodium silicate aqueous solution, and following embodiment is similar) deionized water is added
In be uniformly mixed；Under agitation, 4 mass parts CaCl are slowly added dropwise2Aqueous solution (mass fraction 10%, " 4 mass parts " table
Show CaCl2CaCl in aqueous solution2For 4 mass parts, following embodiment is similar)；After completion of dropwise addition, persistently stir 2 hours, in oxygen
Change sub- silicon face and forms silicate inorganic polymer；Then artificial graphite, acetylene black and polyacrylic acid is added, is thoroughly mixed
It after uniformly, is coated on Cu foil, drying, cold pressing obtain cathode pole piece, wherein artificial graphite, oxidation Asia silicon, acetylene black (the
The acetylene black of secondary addition), the mass ratio of polyacrylic acid be 76:20:2:2.
Embodiment 2
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
95 mass parts are aoxidized into sub- silicon, 1 mass parts acetylene black and 3 mass parts sodium silicate aqueous solutions (mass fraction 20%)
It is added in deionized water and is uniformly mixed；Under agitation, 1 mass parts CaCl is slowly added dropwise2(mass fraction is aqueous solution
10%)；It after completion of dropwise addition, persistently stirs 2 hours, to aoxidize sub- silicon face formation silicate inorganic polymer；Then it is added
Artificial graphite, acetylene black and polyacrylic acid after being thoroughly mixed uniformly, are coated on Cu foil, drying, cold pressing are born
Pole pole piece.Wherein, artificial graphite, aoxidize sub- silicon, acetylene black (second of the acetylene black being added), polyacrylic acid mass ratio be
76:20:2:2。
Embodiment 3
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
75 mass parts are aoxidized into sub- silicon, (mass fraction is for 10 mass parts acetylene blacks and 10 mass parts sodium silicate aqueous solutions
20%) it pours into deionized water and is uniformly mixed；Under agitation, 5 mass parts CaCl are slowly added dropwise2Aqueous solution (mass fraction
For 10%)；It after completion of dropwise addition, persistently stirs 2 hours, to aoxidize sub- silicon face formation silicate inorganic polymer；Then plus
Enter artificial graphite, acetylene black and polyacrylic acid, after being thoroughly mixed uniformly, is coated on Cu foil, drying, cold pressing obtain
Cathode pole piece.Wherein, artificial graphite, aoxidize sub- silicon, acetylene black (second of the acetylene black being added), polyacrylic acid mass ratio be
76:20:2:2。
Embodiment 4
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
70 mass parts are aoxidized into sub- silicon, (mass fraction is for 10 mass parts acetylene blacks and 5 mass parts sodium silicate aqueous solutions
20%) it pours into deionized water and is uniformly mixed；Under agitation, 15 mass parts CaCl are slowly added dropwise2Aqueous solution (mass fraction
For 10%)；It after completion of dropwise addition, persistently stirs 2 hours, to aoxidize sub- silicon face formation silicate inorganic polymer；Then plus
Enter artificial graphite, acetylene black and polyacrylic acid, after being thoroughly mixed uniformly, is coated on Cu foil, drying, cold pressing obtain
Cathode pole piece.Wherein, artificial graphite, aoxidize sub- silicon, acetylene black (second of the acetylene black being added), polyacrylic acid mass ratio be
76:20:2:2。
Embodiment 5
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
70 mass parts are aoxidized into sub- silicon, 25 mass parts sodium silicate aqueous solutions (mass fraction 20%) pour into deionized water
It is uniformly mixed；Under agitation, 5 mass parts CaCl are slowly added dropwise2Aqueous solution (mass fraction 10%)；After completion of dropwise addition,
It persistently stirs 2 hours, to aoxidize sub- silicon face formation silicate inorganic polymer；Then be added artificial graphite, acetylene black and
Polyacrylic acid after being thoroughly mixed uniformly, is coated on Cu foil, drying, cold pressing obtain cathode pole piece.Wherein, artificial stone
Ink, aoxidize sub- silicon, acetylene black, polyacrylic acid mass ratio be 76:20:2:2.
Embodiment 6
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
70 mass parts are aoxidized into sub- silicon, 25 mass parts aluminium phosphate aqueous solutions (mass fraction 20%) pour into deionized water
It is uniformly mixed；Under agitation, 5 mass parts cupric oxide powders are slowly added to；After addition, persistently stir 2 hours, with
It aoxidizes sub- silicon face and forms phosphate inorganic polymer；Then artificial graphite, acetylene black and polyacrylic acid is added, is sufficiently stirred mixed
After closing uniformly, it is coated on Cu foil, drying, cold pressing obtain cathode pole piece.Wherein, artificial graphite, aoxidize sub- silicon, acetylene black,
The mass ratio of polyacrylic acid is 76:20:2:2.
Embodiment 7
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
70 mass parts are aoxidized into sub- silicon, 25 mass parts sodium silicoaluminate aqueous solutions (mass fraction 20%) pour into deionized water
In be uniformly mixed；Under agitation, 5 mass parts CaCl are slowly added dropwise2Aqueous solution (mass fraction 10%)；Completion of dropwise addition
Afterwards, it persistently stirs 2 hours, to aoxidize sub- silicon face formation aluminosilicate inorganic polymer；Then artificial graphite, acetylene is added
Black and polyacrylic acid after being thoroughly mixed uniformly, is coated on Cu foil, drying, cold pressing obtain cathode pole piece.Wherein, people
Make graphite, aoxidize sub- silicon, acetylene black, polyacrylic acid mass ratio be 76:20:2:2.
Embodiment 8
Lithium ion secondary battery is prepared according to method identical with comparative example 1, the difference is that:
(1) preparation of cathode pole piece
70 mass parts are aoxidized into sub- silicon, 25 mass parts ethyl orthosilicates are poured into N-Methyl pyrrolidone and are uniformly mixed；?
Under stirring condition, 5 mass parts NaOH aqueous solutions (mass fraction 10%) are slowly added dropwise；After completion of dropwise addition, it is small persistently to stir 2
When, in the organic derivative for aoxidizing sub- silicon face formation silicate inorganic polymer；Then be added artificial graphite, acetylene black and
Polyacrylic acid after being thoroughly mixed uniformly, is coated on Cu foil, drying, cold pressing obtain cathode pole piece.Wherein, artificial stone
Ink, aoxidize sub- silicon, acetylene black, polyacrylic acid mass ratio be 76:20:2:2.
Next the performance of above-mentioned lithium ion secondary battery is tested.
Test one: the first charge-discharge efficiency test of lithium ion secondary battery
Respectively by the resulting lithium ion secondary battery without charge and discharge of comparative example 1-2 and embodiment 1-8 at normal temperature with
Then 0.1C constant-current charge is lower than 0.05C with 0.3C constant-current charge to 4.2V, then constant-voltage charge to electric current, entirely fills to 3.5V
Charging capacity in electric process is denoted as C1, later with 0.5C constant-current discharge to 2.8V, the discharge capacity of entire discharge process is denoted as
D1。
The first charge-discharge efficiency E=D of lithium ion secondary battery1/C1× 100%.
The first charge-discharge efficiency test result of table 1 comparative example 1-2 and embodiment 1-8
Test two: cathode pole piece rebound test after charging
The thickness test of original state (after being cold-pressed) cathode pole piece: by the cathode pole in comparative example 1-2 and embodiment 1-8
Piece respectively takes 3, tests the thickness of cathode pole piece under original state and is denoted as D0。
The thickness test of cathode pole piece after charging: the lithium ion secondary battery in comparative example 1-2 and embodiment 1-8 is respectively taken
3, at normal temperature with 0.5C constant-current charge to 4.2V, then with 4.2V constant-voltage charge to electric current be lower than 0.05C, be at 4.2V
Fully charged state.Lithium ion secondary battery dismantling after completely filling, tests the thickness of cathode pole piece and is denoted as D1。
Thickness swelling ε=(D of cathode pole piece after charging1-D0)/D0× 100%.
The cathode pole piece rebound test result of table 2 comparative example 1-2 and embodiment 1-8
Test three: the discharge-rate performance test of lithium ion secondary battery
Respectively by comparative example 1-2 and the resulting lithium ion secondary battery of embodiment 1-8 at normal temperature with 0.5C constant-current charge
Be lower than 0.05C to 4.2V, then with 4.2V constant-voltage charge to electric current, later respectively by different discharge-rate (0.2C, 0.5C,
1.0C, 3.0C, 5.0C) it is discharged to 2.8V, electric discharge capacity is worth (i.e. on the basis of the resulting discharge capacity of 0.2C electric discharge
100%).
The discharge-rate the performance test results of table 3 comparative example 1-2 and embodiment 1-8
Test four: the high-temperature storage performance test of lithium ion secondary battery
Comparative example 1-2 and every group of the resulting lithium ion secondary battery of embodiment 1-8 are taken 3, carry out high temperature storage
It can test.
Under room temperature, lithium ion secondary battery is subjected to constant current and constant-voltage charge under the charging current of 1C, until above rationing the power supply
Pressure is 4.2V, tests the thickness of lithium ion secondary battery at this time and is denoted as D0, lithium ion secondary battery is then placed on 80 DEG C of perseverances
In incubator, a thickness is tested every taking-up in 4 hours.
Thickness swelling=(N hours lithium ion secondary battery thickness-after lithium ion secondary battery high temperature storage
D0)/D0× 100%.
The high temperature storage of table 4 comparative example 1-2 and embodiment 1-8 expands test result
| 0 hour | 4 hours | 8 hours | 12 hours | |
| Comparative example 1 | 0% | 8.2% | 14.9% | 28.7% |
| Comparative example 2 | 0% | 6.1% | 10.9% | 20.2% |
| Embodiment 1 | 0% | 5.2% | 9.3% | 13.6% |
| Embodiment 2 | 0% | 7.3% | 8.5% | 15.7% |
| Embodiment 3 | 0% | 6.3% | 8.4% | 14.7% |
| Embodiment 4 | 0% | 6.4% | 8.6% | 15.5% |
| Embodiment 5 | 0% | 5.5% | 9.6% | 13.9% |
| Embodiment 6 | 0% | 5.9% | 7.7% | 14.2% |
| Embodiment 7 | 0% | 6.1% | 8.9% | 13.3% |
| Embodiment 8 | 0% | 6.0% | 9.1% | 14.9% |
Test five: the cycle performance test of lithium ion secondary battery
Comparative example 1-2 and every group of the resulting lithium ion secondary battery of embodiment 1-8 are taken 3, carry out cycle performance survey
Examination.
Respectively at room temperature, 45 DEG C, lithium ion secondary battery is subjected to constant current and constant-voltage charge under the charging current of 1C,
Until upper limit voltage be 4.2V, constant-current discharge is then carried out under the discharge current of 0.5C, until final voltage be 2.75V, note
Record the discharge capacity recycled for the first time；Then carry out 800 charging and discharging circulations.
Lithium ion battery circulation volume conservation rate=(discharge capacity of the 800th circulation/discharge capacity recycled for the first time)
× 100%.
The cycle performance test result of table 5 comparative example 1-2 and embodiment 1-8
| Room temperature, 800 capacity retention ratios recycled | The capacity retention ratio of 45 DEG C, 800 times circulations | |
| Comparative example 1 | 73.1% | 68.8% |
| Comparative example 2 | 76.2% | 71.3% |
| Embodiment 1 | 78.1% | 73.1% |
| Embodiment 2 | 77.5% | 72.7% |
| Embodiment 3 | 80.8% | 74.9% |
| Embodiment 4 | 80.1% | 75.2% |
| Embodiment 5 | 78.6% | 73.6% |
| Embodiment 6 | 78.0% | 73.2% |
| Embodiment 7 | 81.3% | 75.4% |
| Embodiment 8 | 80.6% | 75.7% |
From the test result of Tables 1 and 2 can be seen that aoxidize sub- one layer of inorganic polymer layers of silicon face in-stiu coating or
The organic derivative layer of inorganic polymer can promote the first charge-discharge efficiency of battery, illustrate the inorganic polymer layers or inorganic
The organic derivative layer of polymer plays the role of certain promotion SEI film formation, also facilitates ensuring that the high resiliency of SEI film and tough
Property.Inorganic polymer layers can also inhibit to aoxidize the charging expansion of sub- silicon, this is because the polymerizable type small molecule object such as sodium metasilicate
Matter is aoxidizing the polymerization process of sub- silicon face as in-situ polymerization, it can be achieved that the organic derivative of inorganic polymer or inorganic polymer
With aoxidize fitting closely for sub- silicon, and have the characteristics that intensity is big, good toughness, can tolerate that the charging for aoxidizing sub- silicon expands.
Test result from table 3 to table 5 can be seen that aoxidize sub- one layer of inorganic polymer layers of silicon face in-stiu coating or
The organic derivative layer of inorganic polymer can promote the chemical property of battery, the high rate performance of battery, cycle performance, storage
Performance obtains different degrees of improvement.This is because aoxidizing sub- one layer of inorganic polymer layers of silicon face in-stiu coating or inorganic
The organic derivative layer of polymer can tolerate the charging expansion for aoxidizing sub- silicon, improve the knot for aoxidizing sub- silicon in charge and discharge process
Structure stability, and then guarantee to aoxidize the stability of the SEI film of sub- silicon face, while playing protection and aoxidizing sub- silicon, reduce under high temperature
Effect of the electrolyte in the probability for aoxidizing sub- silicon face generation side reaction.It can also be seen that reality from the test result of embodiment 1-8
The comprehensive performance for applying the battery that example 4 is prepared is more excellent, illustrates that the curing agent of appropriate mix amount and silicate help aoxidizing
Sub- silicon face forms quality more preferably inorganic polymer layers, and the conductive agent of appropriate mix amount can further help in improvement oxygen
The electron-transport for changing sub- silicon, further improves the performance of battery.
Claims (10)
1. a kind of composite negative pole material, which is characterized in that including negative electrode material centronucleus and be coated on negative electrode material centronucleus
The clad on surface, the clad include the organic derivative of inorganic polymer or inorganic polymer.
2. composite negative pole material according to claim 1, which is characterized in that the inorganic polymer is selected from silicate inorganic
One or more of polymer, phosphate inorganic polymer, aluminosilicate inorganic polymer.
3. composite negative pole material according to claim 1, which is characterized in that in the composite negative pole material, the packet
The mass content of coating is less than or equal to 40%, it is preferable that the mass content of the clad is 20%.
4. composite negative pole material according to claim 1, which is characterized in that the negative electrode material centronucleus is negative selected from silicon substrate
One or more of pole material, tin base cathode material.
5. composite negative pole material according to claim 1, which is characterized in that also contain conductive agent in the clad.
6. a kind of preparation method of composite negative pole material is used to prepare composite negative pole material of any of claims 1-5
Material, which is characterized in that comprising steps of
Negative electrode material, optional conductive agent are added in polymerizable type small-molecule substance solution, under agitation thereto
Curing agent is added and carries out polymerization reaction, drying removes solvent to get composite negative pole material is arrived after reaction.
7. the preparation method of composite negative pole material according to claim 6, which is characterized in that
The polymerizable type small-molecule substance is selected from inorganic silicate, inorganic phosphate, inorganic aluminate, ethyl orthosilicate, height
One or more of ridge soil.
8. a kind of cathode pole piece, comprising:
Negative current collector；And
Negative electrode active material layer, on the surface of negative current collector；
It is characterized in that, the negative electrode active material layer includes composite negative pole material according to any one of claims 1-5
Material.
9. cathode pole piece according to claim 8, which is characterized in that the negative electrode active material layer further includes carbon based negative electrodes
Material, conductive agent and binder.
10. a kind of battery, which is characterized in that including the cathode pole piece according to any one of claim 8-9.
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