CN101447561B - Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including the same - Google Patents
Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including the same Download PDFInfo
- Publication number
- CN101447561B CN101447561B CN2008101807258A CN200810180725A CN101447561B CN 101447561 B CN101447561 B CN 101447561B CN 2008101807258 A CN2008101807258 A CN 2008101807258A CN 200810180725 A CN200810180725 A CN 200810180725A CN 101447561 B CN101447561 B CN 101447561B
- Authority
- CN
- China
- Prior art keywords
- negative pole
- polymer
- hydrogen
- pole according
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
A negative electrode for a rechargeable lithium battery and a rechargeable lithium battery including the same are provided. The negative electrode for a rechargeable lithium battery includes a current collector, and a negative active material layer on the current collector. The negative active material layer includes an interpenetrating network, and a negative active material in the interpenetrating network. The interpenetrating network is formed by cross-linking a first polymer having a hydroxyl or amine group and a second polymer having a carboxylic acid group. The negative electrode for a rechargeable lithium battery minimizes volume expansion and imparts good cycle-life characteristics and initial formation efficiency.
Description
Technical field
The present invention relates to a kind of lithium rechargeable battery with negative pole with comprise the lithium rechargeable battery of this negative pole.
Background technology
Lithium rechargeable battery receives publicity as small portable used for electronic device power supply recently.Lithium battery adopts organic electrolyte solution, thereby discharge voltage is the twice that adopts the conventional batteries of alkaline aqueous solution.Therefore, lithium rechargeable battery has high energy density.
Lithium-transition elements the composite oxides that can embed lithium are LiCoO for example
2, LiMn
2O
4, LiNi
1-xCo
xO
2(wherein 0＜x＜1) etc. has been carried out research as lithium rechargeable battery with positive electrode active materials.
Variously can embed carbon class material with the de-embedding lithium ion for example Delanium, native graphite and hard carbon have been used as negative material.Have lower discharge potential owing to comparing with lithium (for example 0.2V), graphite can increase the discharge voltage and the energy density of battery.
Use graphite to have high average discharge potential (for example 3.6V) as the battery of negative active core-shell material.In addition, graphite is because its reciprocal characteristics can be given excellent cycle life, and therefore graphite is more commonly used in above-mentioned carbon class material.Yet the density of graphite is low, thereby the energy capacity of per unit volume is low when it is used as negative active core-shell material.And then when reacting with organic electrolyte under high discharge voltage, graphite can produce and expand or capacity reduces.
For example oxide of other materials has been proposed, more specifically tin oxide, lithium vanadium type oxide etc.Yet, utilize such negative pole battery performance not to be shown sufficient improvement with oxide, therefore still the oxide cathode material is studied in continuation.
Summary of the invention
In one embodiment, the invention provides a kind of lithium rechargeable battery negative pole that is initialized to efficient and cycle life characteristics with improvement.
In another embodiment, the invention provides a kind of lithium rechargeable battery that comprises above-mentioned negative pole.
According to an embodiment of the invention, described negative pole comprises collector and the anode active material layer that is arranged on the described collector.Described anode active material layer comprises the negative active core-shell material in interpenetrating networks and the described interpenetrating networks.
Described interpenetrating networks can carry out crosslinked formation by first polymer that will have hydroxyl or amido and second polymer with carboxyl.
Described interpenetrating networks may further include and are used for carrying out crosslinked terpolymer with first and second polymer, and described terpolymer is rubber-like or fluorinated polymer.
According to another implementation of the invention, provide a kind of lithium rechargeable battery, it comprises above-mentioned negative pole, positive pole and electrolyte.
When negative pole of the present invention was used in the lithium battery, because negative active core-shell material demonstrates the change in volume of reduction, it can improve the cycle life characteristics of lithium battery.In addition, because the reaction of electrolyte and lithium ion wherein is reduced or is minimized, it can improve formation efficiency.Because negative pole has the flexible of increase, thereby can prevent the electrode breakage, the lithium battery that has negative pole of the present invention thus can have high capacity.And then the elasticity of negative pole can increase adhesion strength, thereby can prevent that active material from separating from electrode.
Description of drawings
Accompanying drawing is in conjunction with the illustrative embodiments of the present invention of having described illustration in detail, and comes together to explain principle of the present invention with specification.
Fig. 1 is the schematic diagram according to the lithium rechargeable battery of an embodiment of the invention.
Fig. 2 for expression comprise negative pole according to embodiments of the invention 1, according to the chart of the initial charge/discharge characteristic of the battery unit of the negative pole of Comparative Examples 1.
Fig. 3 for expression comprise negative pole according to embodiments of the invention 1, according to the chart of the discharge capacitance of the battery unit of the negative pole of Comparative Examples 1.
Fig. 4 for expression comprise negative pole according to embodiments of the invention 1, according to the chart of the discharge capacitance of the battery unit of the negative pole of Comparative Examples 1～4.
Fig. 5 for expression comprise negative pole according to embodiments of the invention 1, according to the chart as the coulombic efficiency of cycle-index function of the battery unit of the negative pole of Comparative Examples 1,2 and 4.
Fig. 6 for expression comprise negative pole according to embodiments of the invention 1, according to the chart of the hot strength of the negative pole of Comparative Examples 1 and 2.
Fig. 7 A and 7B represent respectively according to the negative pole of embodiments of the invention 1, according to the solvent resistance curve of the negative pole of Comparative Examples 1.
Embodiment
Usually lithium rechargeable battery can comprise metal species active material, for example Si, Sn etc. with negative active core-shell material.Yet owing to react with lithium, the metal species active material has bigger change in volume, thereby may lose conductive network, causes the deterioration of active material and the reduction of capacity.
Therefore, for example Kynoar, butadiene-styrene rubber etc. are unsuitable for using together with the negative active core-shell material with larger volume variation typical adhesive.
Correspondingly, for example polyimide or polyamideimides adhesive have been suggested to substitute to polymer adhesive.Though having favorable mechanical, these polymer stretch and adhesion strength, their meetings and lithium ion generation electrochemical reaction, thus but reduce the formation efficiency of negative pole and the reverse efficiency under each circulation.
Therefore, the invention provides a kind of negative pole that comprises polymer adhesive, this polymer adhesive have high hardness and with lithium ion have low reactive or do not react suppressing or to reduce the change in volume of negative active core-shell material, thereby improve cycle life characteristics.Negative active core-shell material also has the electrochemical reaction between minimizing or electrolyte that reduces and lithium ion, and has the starting efficiency of improvement.
Negative pole according to an embodiment of the invention comprises collector and the anode active material layer that is arranged on this collector.This anode active material layer comprises the negative active core-shell material in interpenetrating networks and these interpenetrating networks.
Above-mentioned interpenetrating networks can carry out crosslinked formation by first polymer that will have hydroxyl or amido and second polymer with carboxyl.These interpenetrating networks may further include by the condensation reaction and first and second polymer and carry out crosslinked terpolymer, and described terpolymer is rubber-like or fluorinated polymer.
Terpolymer can provide flexible by anticathode.When first, second forms interpenetrating networks with terpolymer by condensation reaction, the change in volume that negative active core-shell material has minimizing or reduces.This may be because second polymer wherein provides firm or hard structure.Because the flexible and elasticity that terpolymer provides, interpenetrating networks also have the adhesion strength of increase to collector.Therefore, interpenetrating networks can prevent active material and electrode separation, and prevent breakage, thereby the battery of high power capacity is provided.
Since interpenetrating networks not with lithium ion generation electrochemical reaction, thereby it can suppress the electrochemical reaction of electrolyte and lithium ion, and improves the formation efficiency of negative pole.
And then interpenetrating networks have high intensity.In one embodiment, the hot strength of interpenetrating networks is greater than 40MPa.In another embodiment, its hot strength is in 40～200MPa scope.In another execution mode, its hot strength is in 50～150MPa scope.When hot strength was in above-mentioned scope, interpenetrating networks can be suppressed at the volumetric expansion of negative active core-shell material in the charge and discharge cycles effectively.When hot strength during less than 40MPa, interpenetrating networks can not suppress the volumetric expansion of negative active core-shell material fully.
In addition, interpenetrating networks have solvent resistance to water and organic solvent.Particularly, interpenetrating networks have the solvent resistance less than 5%.Solvent resistance is by in the water or organic solvent that test electrode are immersed specified quantitative, measures from the amount of the polymeric material of elution wherein and measures.The amount of polymeric material can be by utilizing 1H-NMR quantitative analysis or measure in the solvent as the concentration of ordinary dissolution of the cross-linked polymer adhesive of residue by thermogravimetry (TGA) and to determine.Lower concentration of ordinary dissolution means good solvent resistance.
The solvent resistance of interpenetrating networks also can followingly be investigated: electrode is immersed the regulation or the scheduled time in water or the organic solvent, and lip-deep variation of measurement electrode and adhesion strength.In each execution mode, after electrode was dipped in water or the organic solvent, the adhesion strength of electrode did not worsen, and lip-deep active material does not separate owing to expanding yet.
In one embodiment, interpenetrating networks carry out cross-linking reaction by first and second polymer with the mol ratio in 95:5～20:80 scope and form.In another embodiment, the mol ratio that interpenetrating networks can 80:20～40:60 scope forms.When converting mol ratio to weight ratio, if first and second polymer have identical weight average molecular weight (for example 100,000), then mol ratio is identical with weight ratio.When the weight average molecular weight of first polymer is that the weight average molecular weight of 100,000, second polymer is 20,000 o'clock, mol ratio 95:5 is equivalent to weight ratio 90.5:9.5.Higher and when exceeding above-mentioned mol ratio, the flexible of electrode may worsen when the amount of second polymer.When comprising a spot of second polymer, the hydroxyl of first polymer (OH) or amido (NH
2) the electrochemical decomposition reaction may take place and produce byproduct gas, thereby can reduce battery capacity and efficient.
When using rubber-like or fluorinated terpolymer, the total moles of first and second polymer and the mol ratio of terpolymer can be 95:5～60:40 scope.When comprising rubber-like or fluorinated terpolymer, it may influence the hardness of interpenetrating networks, thereby influences negative pole when excessive.This negative pole may not tolerate the change in volume of negative active core-shell material, and may have the impedance of increase, and this impedance meeting worsens conductive characteristic.When comprising the terpolymer of the amount littler than above-mentioned scope, the flexible and adhesion strength of negative pole may reduce, thereby causes bottom damaged easily.
The suitable example of first polymer is to have hydroxyl or amido and have at least one polymer by the repetitive of following structural formula 1～3 expression.
Structural formula 1
R wherein
1And R
4Be independently selected from respectively in the group that constitutes by C1～C4 alkylidene and alkylene oxide group.In one embodiment, R
1And R
4Be selected from respectively by-CH
2CH
2O-,-CH
2CH (CH
3) O-and-CH
2In the group that O-constitutes.
R
2And R
3Be independently-(CRR ') respectively
n-, wherein R and R ' difference are hydrogen or C1～C5 alkyl independently, n is the integer in 1～4 scope, or more specifically is 1～2.In one embodiment, R
2And R
3Be respectively hydrogen or methyl.
X and Y are independently selected from alkali metal respectively.In one embodiment, X and Y are Na and/or K.
R wherein
5～R
7And R
10Be independently selected from respectively by in hydrogen and the group that C1～the C5 alkyl constitutes.In one embodiment, R
5～R
7Be respectively hydrogen or methyl.
R
8For-(CRR ')
n-(R in one embodiment,
8For-CH
2-), wherein R and R ' are independently selected from respectively by in hydrogen and the group that C1～the C5 alkyl constitutes (in one embodiment, R and R ' difference are hydrogen or methyl independently), and n is the integer in 0～4 scope, or more specifically is 1～2.
R
9And R
11Be independently selected from respectively by hydrogen, C1～C5 alkyl and-(CRR ')
nIn the group that OR ＂ constitutes, wherein R, R ' and R ＂ are hydrogen or C1～C5 alkyl respectively independently, and n is the integer in 1～4 scope.
R
12For-OCOZ, wherein Z can be alkali metal.In one embodiment, Z is Na or K.
M is in 0.1～1 scope.
R wherein
13, R
15And R
17～R
22Be independently-(CRR ') respectively
n-, R and R ' difference are hydrogen or C1～C5 alkyl independently here, n is the integer in 1～4 scope.
R
14And R
16Be independently-[(CRR ') respectively
p-(NH)]
q-, wherein R and R ' difference are hydrogen or C1～C5 alkyl independently, and p is the integer in 1～4 scope, and q is the integer in 1～2 scope.
The non-limitative example of the first suitable polymer comprises carboxymethyl cellulose, polyvinyl alcohol, the copolymer of vinyl alcohol and vinylacetate, vinyl alcohol and cinnamic copolymer, the copolymer of vinyl alcohol and methyl methacrylate, the copolymer of vinyl alcohol and methyl acrylate, the copolymer of vinyl alcohol and EMA, the copolymer of vinyl alcohol and ethyl acrylate, the copolymer of vinyl alcohol and butyl acrylate, the copolymer of vinyl alcohol and butyl methacrylate, polymine and their mixture.
The weight average molecular weight of first polymer (Mw) is 1000～1,000,000 scope.In another embodiment, its weight average molecular weight (Mw) can be 50,000～200,000 scope.When its weight average molecular weight less than 1000 the time, the viscosity that is used to form the slurry of electrode may worsen.When its weight average molecular weight greater than 1,000,000 o'clock, the solvability of solvent may worsen.
Second polymer can be to have the polymer that can carry out crosslinked carboxyl with the hydroxyl or the amido of first polymer.Second polymer can be the compound that comprises the repetitive of following structural formula 4.
R wherein
23～R
25And R
28Be hydrogen or C1～C5 alkyl independently respectively.In one embodiment, R
23～R
25And R
28Be hydrogen or methyl independently respectively.
R
26For-(CRR ')
n-(R in one embodiment,
26For-CH
2-), wherein R and R ' difference are hydrogen or C1～C5 alkyl independently, n is the integer in 0～4 scope.
R
27And R
29Be independently selected from respectively by hydrogen, C1～C5 alkyl and-(CRR ')
nIn the group that OR ＂ constitutes, wherein R, R ' and R ＂ are hydrogen or C1～C5 alkyl respectively independently, and n is the integer in 1～4 scope.
R
30For-OCOZ, wherein Z is an alkali metal.
Z satisfies 0＜z≤1, and in one embodiment, z is in 0.1～1 scope.
The non-limitative example of the second suitable polymer comprises copolymer of copolymer, (methyl) acrylic acid and (methyl) butyl acrylate of poly-(methyl) acrylic acid, (methyl) acrylic acid and (methyl) ethyl acrylate and their mixture.Here, term " poly-(methyl) acrylic acid " is meant polyacrylic acid or polymethylacrylic acid.
The weight average molecular weight of second polymer (Mw) is 1000～1,000,000 scope.In one embodiment, its weight average molecular weight (Mw) can be 50,000～200,000 scope.When its weight average molecular weight less than 1000 the time, the slurry that is used to form electrode may have lower viscosity, thereby is difficult to form electrode.When its weight average molecular weight greater than 1,000,000 o'clock, slurry may have relatively poor solvability in solvent, and crosslinked in electrode may be insufficient.
In one embodiment, first and second polymer are water miscible, in the time of in being formed on anode active material layer, its can be dissolved in the water and and in the non-organic solvent.
The non-limitative example of suitable rubber-like terpolymer comprises butadiene-styrene rubber (SBR), acrylonitrile-butadiene rubber (NBR), methyl methacrylate butadiene rubber, chloroprene rubber, carboxy-modified butadiene-styrene rubber, modified polyorganosiloxanes base polymer and their combination.In one embodiment, butadiene-styrene rubber suits.
The non-limitative example of suitable fluorinated terpolymer comprises the copolymer of Kynoar (PVdF), vinylidene chloride and hexafluoropropylene etc.In one embodiment, Kynoar suits.
In each execution mode, negative active core-shell material is dispersed in the interpenetrating networks.
The non-limitative example of suitable negative active core-shell material comprise the lithium metal, can with lithium form alloy metal material, transition elements oxide, can reversibly mix with lithium and conciliate the material, the material that can reversibly form lithium-containing compound that mix, can reversibly embed and the material of de-embedding lithium ion etc.
Suitable can comprise Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and their combination with the non-limitative example that lithium forms the metal material of alloy.Suitable transition elements oxide, can comprise vanadium oxide, lithium-barium oxide, Si, SiO with the lithium non-limitative example of conciliating the material that mixes or can reversibly form the material of lithium-containing compound that reversibly mixes
x(wherein 0＜x＜2), Si-Y alloy (wherein Y is being selected from by the element in alkali metal, alkaline-earth metal, IIIA family element, IVA family element, transition elements, rare earth element and their group that constitutes except that Si), Sn, SnO
2, Sn-Y (wherein Y is being selected from by the element in alkali metal, alkaline-earth metal, IIIA family element, IVA family element, transition elements, rare earth element and their group that constitutes except that Sn), Titanium Nitrate etc.Above-mentioned negative active core-shell material at least a can with SiO
2In conjunction with.In one embodiment, element Y can be selected from by in Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Ti, Ge, Sn, P, As, Sb, Bi, S, Se, Te, Po and their group that constitutes.
The suitable non-limitative example that can reversibly embed with the material of de-embedding lithium ion comprises any carbon class negative active core-shell material that adopts usually, for example crystalline carbon, amorphous carbon or their mixture in Lithuim rechargeable battery.That the non-limitative example of suitable crystalline carbon comprises is amorphous, tabular, thin slice, spherical or fibrous native graphite or Delanium.The example of suitable amorphous carbon comprises soft carbon (low-temperature sintering carbon) or hard carbon, mesophase pitch carbide, calcined coke etc.
In one embodiment, negative active core-shell material is selected from by Si, SiO
x(wherein 0＜x＜2), Sn, SnO
2And in the group of their mixture formation.
With respect to the total weight of anode active material layer, can comprise the negative active core-shell material of the amount of 80～99wt% scope.In one embodiment, with respect to the total weight of anode active material layer, comprise the negative active core-shell material of the amount of 90～96wt% scope.When the amount of negative active core-shell material during, can not realize the negative pole of high power capacity less than 80wt%.When greater than 99wt%, the amount of binder in the negative pole is not enough to provide suitable adhesion strength between negative active core-shell material and collector.
Above-mentioned have the anode active material layer that is dispersed in the negative active core-shell material in the interpenetrating networks and may further include other components that are selected from the group that is made of conductive agent, crosslinking agent and their mixture.
Only otherwise can cause chemical change, any electric conducting material can both be used as conductive agent.The non-limitative example of suitable conductive agent comprises native graphite, Delanium, carbon black, acetylene black, Kai Qinhei (ketjenblack), carbon fiber, polyphenylene derivative, comprises copper, the metal dust of nickel, aluminium, silver or metallic fiber etc.
Can also use other conductive agents well known in the art, and can control consumption according to application target.
First and second polymer and selectable terpolymer can be undertaken crosslinked by the thermal condensation reaction, but also can adopt other reaction methods, for example utilize crosslinking agent to promote cross-linking reaction.
When anode active material layer had above-mentioned composition, it can have excellent adhesion strength to collector.Adhesion strength to collector can be in 0.05N/mm～0.2N/mm scope.In another embodiment, adhesion strength is in 0.1N/mm～0.2N/mm scope.
In one embodiment, anode active material layer is formed on the collector.
Collector can be selected from by Copper Foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foams, be coated with in the polymeric material and their group that constitutes of conducting metal.
When above-mentioned anode active material layer and collector were made into negative pole, negative pole was exposed to electrolyte solution and by after this solution infiltration, this negative pole has less thickness swelling in the battery charging and discharging circulation.The varied in thickness of negative pole can be calculated according to following formula 1.Negative pole is exposed to electrolyte solution and by after the infiltration of this solution, this negative pole on thickness increase or change less than 40%.In another embodiment, increase or the variation of this negative pole on thickness can be preferably in 1～10% scope in 1～30% scope, more preferably in 1～5% scope.
Formula 1:
Negative pole is in the variation on the thickness or expansion rate (%)=[(negative pole be exposed to electrolyte solution and by the thickness of thickness-negative pole before infiltration after this solution infiltration)/thickness of negative pole before infiltration] * 100
Above-mentioned negative pole can followingly be made: preparation is used to form the composition of active material layer, and said composition comprises first and second polymer and negative active core-shell material; Form active material layer by coating said composition on collector, and the collector after the coating is heat-treated; Then it is carried out vacuum heat.
Below manufacture method will be described in more detail.At first, first and second polymer and negative active core-shell material are dispersed or dissolved in the solvent, prepare the composition that is used to form active material layer.Can comprise terpolymer in addition.
The type of first and second polymer, selectable terpolymer and negative active core-shell material can be with previously described identical with amount.
First and second polymer and selectable terpolymer can solid or the solution form be provided.When providing as solution, first, second and third polymer is owing to be water miscible, and it is dissolved in the solvent.
The composition that is used to form active material layer can be dissolved in water-soluble solvent for example in the water.Can determine and regulate the amount of solvent, make specific viscosity, coating and the printing characteristic of active material layer to realize.
The composition that is used to form active material layer can comprise additive, and this additive is selected from by the conductive agent that improves conductivity, promote in the group that crosslinked crosslinking agent and their mixture constitute.
The composition that is used to form active material layer is coated on the collector, is heated, vacuum heat, to form anode active material layer.
According to the viscosity of composition, the non-limitative example of the method for suitable coating composition comprises that silk screen print method, spraying rubbing method, scraper rubbing method, intaglio plate rubbing method, dip coated method, silk screen cover method, covering with paint method and channel mould rubbing method.
Collector is same as described above.
In one embodiment, the composition that is used to form active material layer is coated on the collector, and heat-treats under the temperature of 80～120 ℃ of scopes.In another embodiment, can under the temperature of 90～110 ℃ of scopes, heat-treat with evaporation and be used to form solvent in the composition of active material layer.When heat-treating under being lower than 80 ℃ temperature, solvent can not be evaporated fully.When heat-treating under being higher than 120 ℃ temperature, solvent is volatilization fast, generates thereby accelerate gas, makes the surface uniformity variation of electrode.In certain execution mode, the evaporation of solvent or drying can be carried out under atmospheric conditions.
After solvent in the composition that is used to form active material layer on being coated on collector is evaporated by heat treatment, can under vacuum, carry out the heat treatment second time.
In one embodiment, heat treatment for the second time is under the temperature of 130～200 ℃ of scopes, carry out under vacuum.In another embodiment, heat treatment for the second time can be carried out under the temperature of 150～200 ℃ of scopes, to bring out in the composition condensation reaction of first, second and selectable terpolymer.The condensation reaction of first, second and selectable terpolymer occurs in second heat treatment process, can form crosslinked and produces water.The water that produces is evaporated by heat treatment.When under the heat treatment second time is being lower than 130 ℃ temperature, carrying out, can not carry out condensation reaction fully.When carrying out under the heat treatment second time is being higher than 200 ℃ temperature, the adhesive in the electrode may decompose.
Heat treatment for the second time can be carried out under vacuum.Vacuum pressure can be less than 1 * 10
-4Holder.The pneumatics power of taking seriously is higher than 1 * 10
-4During holder, coating can not suitably be bonded on the collector.In one embodiment, vacuum pressure is 1 * 10
-4～1 * 10
-6The holder scope.In another embodiment, vacuum pressure is 5 * 10
-5～1 * 10
-6The holder scope.
Based on above-mentioned manufacture method, the anode active material layer that is formed on the collector can be provided, and this anode active material layer comprises the interpenetrating networks that form by crosslinked first, second and selectable terpolymer and is distributed in negative active core-shell material in the network.
When above-mentioned negative pole was used in the lithium rechargeable battery, the cross-linked network in the active material layer can suppress or prevent change in volume, thereby improved the battery cycle life characteristic.In addition, negative pole of the present invention can suppress the electrochemical reaction of electrolyte and lithium ion, thereby improves the formation efficiency of negative pole.And when further comprising terpolymer, it can strengthen the flexible and elasticity of cross-linked network, thereby increases adhesion strength.And then when active material layer formed thickness sufficient, electrode can be not damaged, and the battery with high power capacity is provided thus.
According to another implementation of the invention, provide the lithium rechargeable battery that comprises above-mentioned negative pole.
According to the type of dividing plate that uses in the battery and electrolyte, lithium rechargeable battery can be divided into lithium ion battery, lithium ion polymer battery and lithium polymer battery.Lithium rechargeable battery can form different shape and size, and for example cylindrical, prismatic or Coin-shape cell can be film or bulky battery.About the structure and the manufacture method of lithium ion battery of the present invention is being known in the art, therefore it is not carried out detailed discussion.
Fig. 1 is the decomposition diagram according to the lithium rechargeable battery of an embodiment of the invention.Fig. 1 shows the structure according to the cylindrical battery of an embodiment of the invention, but battery of the present invention is not limited to the structure of Fig. 1.Battery according to an embodiment of the invention can be prismatic or pouch-type battery.
Fig. 1 illustration cylindrical lithium rechargeable battery 100, it comprises negative pole 112, anodal 114, the seal 140 that is inserted in electrolyte, battery case 120 and the sealed cell shell 120 of dividing plate 113 between negative pole 112 and anodal 114, dipping dividing plate 113.Lithium rechargeable battery 100 following formation: negative pole 112, positive pole 114 and dividing plate 113 are piled up, spirally it is reeled, be inserted into then in the battery case 120.
Anode active material layer can comprise positive electrode active materials, for example can reversibly embed the lithium intercalation compound with the de-embedding lithium ion.Particularly, positive electrode active materials can comprise the compound of following structural formula 5～29.
Li
aA
1-bX
bD
2，
Wherein, 0.95≤a≤1.1 and 0≤b≤0.5.
Li
aE
1-bX
bO
2-cM
c，
Wherein, 0.95≤a≤1.1,0≤b≤0.5 and 0≤c≤0.05.
Structural formula 7
LiE
2-bX
bO
4-cM
c，
Wherein, 0≤b≤0.5 and 0≤c≤0.05.
Li
aNi
1-b-cCo
bX
cD
α，
Wherein, 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0＜α≤2.
Structural formula 9
Li
aNi
1-b-cCo
bX
cO
2-αM
α，
Wherein, 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0＜α＜2.
Li
aNi
1-b-cCo
bX
cO
2-αM
2，
Wherein, 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0＜α＜2.
Structural formula 11
Li
aNi
1-b-cMn
bX
cD
α，
Wherein, 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0＜α≤2.
Structural formula 12
Li
aNi
1-b-cMn
bX
cO
2-αM
α，
Wherein, 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0＜α＜2.
Structural formula 13
Li
aNi
1-b-cMn
bX
cO
2-αM
2，
Wherein, 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0＜α＜2.
Structural formula 14
Li
aNi
bE
cG
dO
2，
Wherein, 0.90≤a≤1.1,0≤b≤0.9,0≤c≤0.9 and 0.001≤d≤0.1.
Li
aNi
bCo
cMn
dG
eO
2，
Wherein, 0.90≤a≤1.1,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5 and 0.001≤e≤0.1.
Structural formula 16
Li
aNiG
bO
2，
Wherein, 0.90≤a≤1.1 and 0.001≤b≤0.1.
Structural formula 17
Li
aCoG
bO
2，
Wherein, 0.90≤a≤1.1 and 0.001≤b≤0.1.
Structural formula 18
Li
aMnG
bO
2，
Wherein, 0.90≤a≤1.1 and 0.001≤b≤0.1.
Structural formula 19
Li
aMn
2G
bO
4，
Wherein, 0.90≤a≤1.1 and 0.001≤b≤0.1.
QO
2
Structural formula 21
QS
2
Structural formula 22
LiQS
2
Structural formula 23
V
2O
5
Structural formula 24
LiV
2O
5
LiZO
2
Structural formula 26
LiNiVO
4
Structural formula 27
Li
(3-f)J
2(PO
4)
3(wherein, 0≤f≤3)
Structural formula 28
Li
(3-f)Fe
2(PO
4)
3(wherein, 0≤f≤2)
Structural formula 29
LiFePO
4
In said structure formula 5～29, A is selected from by in Ni, Co, Mn and their group that constitutes; X is selected from by in Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth element and their group that constitutes; D is selected from by in O, F, S, P and their group that constitutes; E is selected from by in Co, Mn and their group that constitutes; M is selected from by in F, S, P and their group that constitutes; G is selected from by in Al, Cr, Mn, Fe, Mg, Sr, V, lanthanide series and their group that constitutes, and this lanthanide series for example is La, Ce; Q is selected from by in Ti, Mo, Mn and their group that constitutes; Z is selected from by in Cr, V, Fe, Sc, Y and their group that constitutes; J is selected from by in V, Cr, Mn, Co, Ni, Cu and their group that constitutes.
In addition, positive electrode active materials can comprise inorganic sulfur (S
8, elementary sulfur) and the sulfur-bearing compounds.The sulfur-bearing compounds can comprise Li
2S
n(wherein, n 〉=1), be dissolved in the Li in the catholyte
2S
n(wherein, n 〉=1), organosulfur compound, carbon-sulphur polymer ((C for example
2Sf)
n, wherein, 2.5≤f≤50 and n 〉=2) etc.
Positive electrode active materials can comprise the positive electrode active materials of coating form or with coating applied active material mixture and active material.
The non-limitative example of suitable coating comprises oxide and hydroxide, the oxyhydroxide of coating element, the subcarbonate of coating element and the hydroxyl carbonate of coating element that is coated with element.The compound that is used for coating can be amorphous state or crystalline state.The non-limitative example of suitable coating element comprises Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr and their combination.
Coating process can be to well known to a person skilled in the art any existing method, as long as it can not produce any negative effect (for example spraying coating, dipping) to the performance of positive electrode active materials, has therefore omitted detailed description.
Anode active material layer may further include adhesive and conductive agent.
Adhesive be used to improve between the positive electrode active materials particle with and to the adhesive property of collector.The non-limitative example of suitable adhesive comprises polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylation polyvinyl chloride, polyvinyl fluoride, contains ethylene oxide polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, butadiene-styrene rubber, propylene acidifying butadiene-styrene rubber, epoxy resin, nylon etc.
Conductive agent is used to improve anodal conductivity.As long as it can not produce chemical change, any electric conducting material can be used as conductive agent.The non-limitative example of suitable conductive agent comprises native graphite, Delanium, carbon black, acetylene black, Kai Qinhei, polyphenylene derivative, carbon fiber, comprises copper, the metal dust of nickel, aluminium, silver or metallic fiber etc.
A non-limitative example of suitable collector is Al.
In one embodiment, electrolyte comprises non-aqueous organic solvent and lithium salts.
Non-aqueous organic solvent serves as the medium of the ion that is used to transmit the electrochemical reaction that participates in battery.
The non-limitative example of suitable non-aqueous organic solvent comprises carbonates, ester class, ethers, ketone, alcohols and aprotic solvent.The non-limitative example of suitable carbonates solvent comprises dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid methyl propyl ester (MPC), carbonic acid ethyl propyl ester (EPC), carbonic acid methyl ethyl ester (MEC), carbonic acid ethyl methyl esters (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) etc.The non-limitative example of suitable esters solvent can comprise methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, decalactone, valerolactone, mevalonolactone, caprolactone etc.The non-limitative example of suitable ether solvent comprises butyl oxide, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethoxy-ethane, 2-methyltetrahydrofuran, oxolane etc.The non-limitative example of suitable ketones solvent comprises cyclohexanone etc.The non-limitative example of suitable aprotic solvent comprises for example Z-CN (wherein, Z is linearity, chain or the cyclic hydrocarbon of C2～C20, two key aromatic rings or ehter bond) of nitrile, amide-type is dimethyl formamide for example, dioxolanes for example 1,3-dioxolanes, sulfolane etc.
Non-aqueous organic solvent can use or mix use separately.When mixing with an organic solvent, can be according to the battery performance control or the adjusting blending ratio of expectation.
The carbonates solvent can comprise the mixture of cyclic carbonate and linear carbonates.In one embodiment, cyclic carbonate and linear carbonates are mixed by the volume ratio with 1:1～1:9 scope.When the mixture that obtains is used as electrolyte, can strengthen the performance of electrolyte.
And then non-aqueous organic solvent can comprise the mixture of carbonates solvent and aromatic hydrocarbon solvent.In one embodiment, carbonates solvent and aromatic hydrocarbon solvent are mixed by the volume ratio with 1:1～30:1 scope.
The arene organic solvent can be by following structural formula 30 expressions.
Wherein, R
31～R
36Be independently selected from respectively by in hydrogen, halogen, C1～C10 alkyl, C1～C10 haloalkyl and their group that constitutes.
The non-limitative example of suitable arene organic solvent comprises benzene, fluorobenzene, 1,2-two fluorobenzene, 1,3-two fluorobenzene, 1,4-two fluorobenzene, 1,2, the 3-trifluoro-benzene, 1,2, the 4-trifluoro-benzene, chlorobenzene, 1, the 2-dichloro-benzenes, 1, the 3-dichloro-benzenes, 1, the 4-dichloro-benzenes, 1,2, the 3-trichloro-benzenes, 1,2, the 4-trichloro-benzenes, iodobenzene, 1, the 2-diiodo-benzene, 1, the 3-diiodo-benzene, 1, the 4-diiodo-benzene, 1,2, the 3-triiodo-benzene, 1,2, the 4-triiodo-benzene, toluene, toluene fluoride, 1, the 2-difluoro toluene, 1, the 3-difluoro toluene, 1, the 4-difluoro toluene, 1,2, the 3-benzotrifluoride, 1,2, the 4-benzotrifluoride, chlorotoluene, 1, the 2-dichlorotoleune, 1, the 3-dichlorotoleune, 1, the 4-dichlorotoleune, 1,2, the 3-benzotrichloride, 1,2, the 4-benzotrichloride, iodotoluene, 1,2-two iodotoluenes, 1,3-two iodotoluenes, 1,4-two iodotoluenes, 1,2,3-three iodotoluenes, 1,2,4-three iodotoluenes, dimethylbenzene and their combination.
Nonaqueous electrolytic solution may further include the ethylene carbonate compounds of vinylene carbonate or following structural formula 31 to improve the cycle life characteristics of battery.
Structural formula 31
Wherein, R
37And R
38Be independently selected from respectively by hydrogen, halogen, cyano group (CN), nitro (NO2) and C1～C5 fluorinated alkyl, and R
37And R
38Can not be hydrogen simultaneously.
The non-limitative example of suitable ethylene carbonate compounds comprises carbonic acid two fluoroethylenes, carbonic acid chloro ethyl, carbonic acid dichloro ethyl, carbonic acid bromo ethyl, carbonic acid dibromo ethyl, carbonic acid nitro ethyl, carbonic acid cyano group ethyl, carbonic acid fluoro ethyl etc.The amount of above-mentioned solvent additive can be conditioned to improve cycle life.
Lithium salts is supplied lithium ion in battery, promote the basic operation of lithium rechargeable battery and improve the transmission of lithium ion between positive pole and negative pole.The non-limitative example of suitable lithium salts comprises LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiCF
3SO
3, LiC
4F
9SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiAlO
2, LiAlCl
4, LiN (C
pF
2p+1SO
2) (C
qF
2q+1SO
2) (wherein, p and q are natural number), LiCl, LiI, dioxalic acid lithium borate and their mixture.
Lithium salts can 0.1～2.0M concentration use.When lithium salt during less than 0.1M, electrolyte property may worsen owing to low electrolyte conductivity.When lithium salt during greater than 2.0M, the lithium ion mobility may reduce owing to the increase of electrolyte viscosity.
Lithium rechargeable battery may further include the dividing plate 113 between negative pole 112 and anodal 114.The non-limitative example of the material of suitable dividing plate 113 comprises polyethylene, polypropylene, Kynoar and their polylayer forest, for example polyethylene/polypropylene double-layer clapboard, three layers of dividing plate of polyethylene/polypropylene/polyethylene and three layers of dividing plate of polypropylene, polyethylene/polypropylene.
The following examples have been described the present invention in more detail.Yet these embodiment should not be interpreted as scope of the present invention is limited.
Embodiment 1: the making of negative pole
With silica negative active core-shell material (SHR12, Shin-Etsu Chemical Co., Ltd.) be 90 with the weight average molecular weight (Mw) that is dissolved in the water, 000 carboxymethyl cellulose and the Mw that is dissolved in the water are 100,000 polyacrylic acid mixes, to be provided for forming the composition of active material layer.The mol ratio of calculating with 73.5:26.5 according to dry state provides carboxymethyl cellulose and polyacrylic acid, and the mixture that obtains comprises the silica negative active core-shell material of 93wt%, the carboxymethyl cellulose of 5wt% and the polyacrylic acid of 2wt%.
The composition that is used to form active material layer is screen printed on the Cu collector, heat-treats at 90 ℃ then.Then, be 1 * 10 at 200 ℃, vacuum pressure
-6Holder is heat-treated so that negative pole to be provided once more to it down.
Embodiment 2: the making of negative pole
Silica negative active core-shell material (the SHR12 that in water, mixes 93wt%, Shin-Etsu ChemicalCo., Ltd.), the carboxymethyl cellulose of 4wt%, the polyacrylic acid of 2wt% and the conductive agent Super-P of 1wt%, with the composition (having carboxymethyl cellulose and polyacrylic mixture that mol ratio is 69:31) that is provided for forming active material layer.
The composition that is used to form active material layer is screen printed on the Cu collector, heat-treats at 90 ℃ then.Then, be 1 * 10 at 200 ℃, vacuum pressure
-6Holder is heat-treated so that negative pole to be provided once more to it down.
Comparative Examples 1: the making of negative pole
(SHR 12 for the silica negative active core-shell material of mixing 93wt% in as the N-methyl pyrrolidone of solvent, Shin-Etsu Chemical Co., Ltd.) and the Mw of 7wt% be 400,000 polyamidoimide, be used to form the composition of active material layer with preparation.The composition that is used to form active material layer is screen printed on the Cu collector, carries out drying at 120 ℃ then, so that negative pole to be provided.
Comparative Examples 2: the making of negative pole
Except replacing using as the polyamidoimide of adhesive Mw is beyond 600,000 the Kynoar, according to preparing negative pole with the same method of Comparative Examples 1.
Comparative Examples 3: the making of negative pole
Except the polyacrylic acid of the carboxymethyl cellulose that replaces using 5wt% and 2wt% as the polyamidoimide of rigid polymer as the amorphous polymer, according to preparing negative pole with the same method of Comparative Examples 1.
Comparative Examples 4: the making of negative pole
Except replacing using the carboxymethyl cellulose of 7wt%, according to preparing negative pole with the same method of Comparative Examples 1 as the polyamidoimide of adhesive.
Be used for the making of the battery unit of test battery characteristic
The negative pole of embodiment 1 and Comparative Examples 1 is included in the test battery unit.
Composition as positive electrode active materials is prepared as follows: the LiCoO that mixes average grain diameter 10 μ m according to weight ratio 94:3:3
2, as the Kynoar of adhesive with as the carbon (Super-P) of electric conducting material, the mixture that obtains is dispersed in the N-N-methyl-2-2-pyrrolidone N-.Said composition is coated on the thick aluminium foil of 15 μ m and compacting and provide anodal.
Above-mentioned both positive and negative polarity is reeled with the thick polyethylene separator of 25 μ m and suppress, and inject electrolyte solution so that 18650 cylindrical battery cells to be provided.Electrolyte solution is by the LiPF of dissolving 1mol/L in mixed solvent
6And prepare, this mixed solvent is by preparing with the inferior propyl ester (PC) of the volume ratio mixed carbonic acid of 1:1:1, diethyl carbonate (DEC), ethylene carbonate (EC).
The evaluating characteristics of battery unit
1. charge/discharge capacity and formation efficiency
In changing into charge and discharge process respectively to comprise embodiment 1 and 2 and the test battery unit evaluation of the negative pole of Comparative Examples 1～4 charge/discharge capacity and formation efficiency.The result is illustrated among following table 1 and Fig. 2.
Formation charging by under 0.2C with 4.4V to battery unit charging and be discharged to 2.75V with 0.2C and carry out.
Table 1
| ? | Charging capacity (mAh) | Discharge capacity (mAh) | Formation efficiency (%) |
| Embodiment 1 | ?9.91 | ?7.21 | 73.9 |
| Comparative Examples 1 | ?9.87 | ?6.83 | 69.2 |
Fig. 2 is the chart of expression according to the initial charge/discharge capacity of negative pole in the formation charging process of embodiment 1 and Comparative Examples 1.
As table 1 and shown in Figure 2, the negative pole of the interpenetrating networks that comprise adhesive resin of embodiment 1 has better result at the negative pole than Comparative Examples 1 aspect initial charge/discharge capacity and the formation efficiency.
2. the initial electrode expansion rate is estimated
Behind formation charging, the negative pole of embodiment 1 and Comparative Examples 1 has been estimated the electrode expansion rate.The electrode expansion rate is calculated with thickness of electrode percentage change before and after the formation charging.
The negative pole of embodiment 1 has 30% thickness of electrode expansion rate, and the negative pole of Comparative Examples 1 has 50% thickness of electrode expansion rate.This is that the interpenetrating networks that are comprised in the active material suppress because the negative pole in the negative pole of embodiment 1 expands.
3. cycle life characteristics evaluation
To the test battery unit evaluation of the negative pole that comprises embodiment 1 and Comparative Examples 1 cycle life characteristics.Cycle life characteristics carries out in the current condition and the 4.3V～2.75V scope (once discharging and recharging) of 0.8C～1C scope.Cycle life characteristics is estimated by measuring discharge capacitance.Discharge capacitance is measured with the percentage of the relative initial capacity of capacity after discharging and recharging.The result is illustrated among Fig. 3.
As shown in Figure 3, the negative pole of embodiment 1 has better discharge capacity guarantor than the negative pole of Comparative Examples 1
4. discharge capacitance evaluation
According to the same method in front discharge capacitance as the cycle-index function has been measured in the test battery unit of the negative pole that comprises embodiment 1 and Comparative Examples 1～4.
About the discharge capacitance evaluation, battery unit is charged to 4.4V and is discharged to 2.75V under 25 ℃ of charge rates at 1C.Discharge capacitance is calculated with the percentage of the relative initial capacity of capacity after repeating to discharge and recharge.The result is illustrated among Fig. 4.
As shown in Figure 4, has more excellent discharge capacitance according to the negative pole of the interpenetrating networks that comprise adhesive resin of embodiment 1 than the negative pole of Comparative Examples 1～4.Particularly, comprise carboxymethyl cellulose and the polyacrylic negative pole beguine according to Comparative Examples 3 has better discharge capacitance according to the negative pole that only comprises carboxymethyl cellulose of Comparative Examples 4.Yet, have better discharge capacitance than the negative pole of Comparative Examples 3 according to the negative pole of embodiment 1 with the interpenetrating networks that form by carboxymethyl cellulose and polyacrylic acid.
5. coulombic efficiency evaluation
To the test battery unit evaluation of the negative pole that comprises embodiment 1 and Comparative Examples 1 coulombic efficiency.
Utilize the method identical with discharge capacitance to estimate coulombic efficiency (%), its percentage with the relative charging capacity of discharge capacity is calculated.The result is illustrated among Fig. 5.
As shown in Figure 5, the negative pole with resin interpenetrating network of embodiment 1 has better coulombic efficiency than the negative pole of Comparative Examples 1.Particularly, the negative pole of Comparative Examples 1 has fluctuation on coulombic efficiency.This is because the adhesive resin in the negative pole of Comparative Examples 1 is not with dealing with volumetric expansion, thereby the volume of negative pole can change or expand intensely in charge and discharge cycles.
6. the thickness swelling evaluation of battery unit
The test battery unit that comprises the negative pole of embodiment 1 and Comparative Examples 1 and 2 is charged by the charge rate with 0.1C, and has investigated thickness swelling.
Thickness swelling utilizes formula 2 to calculate.
Formula 2:
Thickness swelling (%)=[(thickness of the preceding negative pole of thickness-injection electrolyte solution of negative pole behind the injection electrolyte solution)/(injecting the thickness of the preceding negative pole of electrolyte solution)] * 100
Statement " after injecting electrolyte solution " is meant the battery unit after the charging, and statement " before injecting electrolyte solution " is meant the battery unit before the charging.
The test battery unit that comprises the negative pole of Comparative Examples 1 and 2 has 40% and 60% thickness swelling respectively, and the test battery unit that comprises the negative pole of embodiment 1 only has 30% thickness swelling.
Electrode performance is estimated
1. adhesion strength evaluation
Negative pole to embodiment 1 and Comparative Examples 1 has been estimated adhesion strength.
Adhesion strength is following to be measured: the negative pole of embodiment 1 and Comparative Examples 1 is pasted the versatile material test machine (can obtain from I NSTRON Co.Ltd.) with single cylinder, peel off current collector layers with 50.0mm/min speed, 180 ° of angles then.
The adhesion strength that records between the collector of Comparative Examples 1 and active material layer is 0.07N/mm, and the adhesion strength of embodiment 1 is 0.1N/mm.
2. hot strength evaluation
Negative pole to embodiment 1 and Comparative Examples 1 and 2 has been measured hot strength.The result is illustrated among Fig. 6.
The hot strength utilization has the versatile material test machine (can obtain from INSTRON Co.Ltd.) of single cylinder and measures under crosshead speed 20.0mm/min.
As shown in Figure 6, Comparative Examples 1 and 2 negative pole have the hot strength of 65MPa and 20MPa respectively, and the negative pole of embodiment 1 has the high tensile of 80MPa.
3. solvent resistance evaluation
Negative pole to embodiment 1 and Comparative Examples 1 has been measured solvent resistance.The result is illustrated among Fig. 7 A and the 7B.
Solvent resistance immerses negative pole before and after the electrolyte solution 12 hours the adhesion strength of negative pole by inquiry and changes and estimate.
Fig. 7 A and 7B are the solvent resistance result's of the negative pole of representing embodiment 1 and Comparative Examples 1 respectively chart.
Shown in Fig. 7 A and 7B, the negative pole of embodiment 1 does not have adhesion strength to change before and after immersing electrolyte solution.Yet the negative pole of Comparative Examples 1 has the adhesion strength of deterioration after immersing electrolyte solution.Therefore, the very a spot of material of the negative pole of embodiment 1 is by the electrolyte solution elution.
The negative pole of embodiment 1 and Comparative Examples 1 and 2 is dipped in the solvent N-methyl pyrrolidone 12 hours, and visualization.
The negative pole of embodiment 1 has very little variation, and the negative pole of Comparative Examples 1 expands, and this is to be separated and cause in negative terminal surface by active material.Similarly, the negative pole of Comparative Examples 2 has relatively poor result because adhesive component fully by elution in the N-methyl pyrrolidone, thereby cause active material to separate from collector.
Embodiment 3: the making of negative pole
Silica negative active core-shell material (can from Shin-Etsu Chemical Co., Ltd. obtain) and the adhesive composition of 7wt% and prepare of the composition that is used to form active material layer by mixing 93wt% equably.This adhesive composition is 90 by mixing Mw with the weight ratio of 1:1:1,000 the carboxymethyl cellulose (CMC), the Mw that are dissolved in the water are 100,000 be dissolved in polyacrylic acid (PAA) in the water and Kynoar (PVdF) (can obtain Hylar Latex 932 from Solvay Company) and prepare.
The composition that is used to form active material layer is screen printed on the Cu collector, heat-treats at 90 ℃ then.Then, be 1 * 10 at 200 ℃, vacuum pressure
-6Holder is heat-treated so that negative pole to be provided once more to it down.
Except using the different binder combination composition formula shown in following table 2, prepare the negative pole of embodiment 4～8 according to method similarly to Example 3.As shown in table 2, embodiment 6～8 comprises butadiene-styrene rubber (SBR).
Table 2 (unit: weight ratio)
| ? | |
|
|
Embodiment 7 | |
| |
4 | 4.5 | 1 | 4 | 4.5 |
| |
4 | 4.5 | 1 | 4 | 4.5 |
| PVdF | 2 | 1 | - | - | - |
| SBR | - | - | 1 | 2 | 1 |
Embodiment 9: the making of negative pole
The composition that is used to form active material layer prepares by the silicon-aluminum of mixing 90wt% and the adhesive composition of 10wt%.This adhesive composition is 13 by mixing Mw with the weight ratio of 5:5:1,000～23, the polyvinyl alcohol (PVA), the Mw that are dissolved in the water of 000 scope are 100,000 be dissolved in polyacrylic acid in the water and Kynoar (PVdF) (can obtain Hylar Latex 932 from Solvay Company) and prepare.
The composition that is used to form active material layer is screen printed on the Cu collector, heat-treats at 90 ℃ then.Then, be 1 * 10 at 200 ℃, vacuum pressure
-6Holder is heat-treated so that negative pole to be provided once more to it down.
Except using the adhesive composition shown in following table 3, prepare the negative pole of embodiment 10～14 according to method similarly to Example 9.As shown in table 3, embodiment 12～14 comprises butadiene-styrene rubber (SBR).
Table 3 (unit: weight ratio)
| ? | |
Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| |
4 | 4.5 | 1 | 4 | 4.5 |
| |
4 | 4.5 | 1 | 4 | 4.5 |
| PVdF | 2 | 1 | - | - | - |
| SBR | - | - | 1 | 2 | 1 |
Embodiment 15: the making of negative pole
Silica negative active core-shell material (can from Shin-Etsu Chemical Co., Ltd. obtain) and the adhesive composition of 20wt% and prepare of the composition that is used to form active material layer by mixing 80wt%.This adhesive composition is 100 by polymine (PEI), the Mw of the even mixed dissolution of weight ratio in water with 1:1:1,000 be dissolved in polyacrylic acid in the water and Kynoar (can obtain Hylar Latex 932 from Solvay Company) and prepare.
The composition that is used to form active material layer is screen printed on the Cu collector, heat-treats at 90 ℃ then.Then, be 1 * 10 at 200 ℃, vacuum pressure
-6Holder is heat-treated so that negative pole to be provided once more to it down.
Embodiment 16～20: the making of negative pole
Except using the different binder combination composition formula shown in following table 4, prepare the negative pole of embodiment 16～20 according to method similarly to Example 15.
Table 4 (unit: weight ratio)
| ? | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | |
| |
4 | 4.5 | 1 | 4 | 4.5 |
| |
4 | 4.5 | 1 | 4 | 4.5 |
| PVdF | 2 | 1 | - | - | - |
| SBR | - | ? | 1 | 2 | 1 |
Comparative Examples 5: the making of negative pole
The Mw that uses 7wt% except replacing polyamidoimide is 90,000 is dissolved in beyond the carboxymethyl cellulose in the water, according to making negative pole with the same method of Comparative Examples 1.
Embodiment 21 and 22: the making of negative pole
Except the adhesive that uses following table 5, make negative pole according to method similarly to Example 3.
Comparative Examples 6～9
Except using different adhesive formula as shown in table 5, and beyond composition do not heat-treat, make the negative pole of Comparative Examples 6～9 according to method similarly to Example 3 under vacuum.
Table 5 (unit: weight ratio)
| ? | CMC | PVA | PAA | SBR | PVdF |
| Embodiment 21 | - | 5 | 5 | - | - |
| Embodiment 22 | 5 | - | 5 | - | - |
| Comparative Examples 6 | 5 | - | - | 5 | - |
| Comparative Examples 7 | - | - | 3 | 1 | - |
| Comparative Examples 8 | - | - | 5 | - | 5 |
| Comparative Examples 9 | - | - | 3 | - | 1 |
Be used for the making of the test battery unit of evaluating characteristics
Making comprises that the battery unit of negative pole of embodiment 3～22 and Comparative Examples 5～9 is to estimate electrochemical properties.
Use the negative pole of embodiment 3,9,15 and 21.
The LiCoO that mixes average grain diameter 10 μ m according to weight ratio 94:3:3
2, as the Kynoar of adhesive with as the carbon (Super-P) of electric conducting material, the mixture that obtains is dispersed in the N-N-methyl-2-2-pyrrolidone N-to form anode active material composition.Said composition is coated on the thick aluminium foil of 15 μ m and compacting and provide anodal.
Above-mentioned both positive and negative polarity is reeled with the thick polyethylene separator of 25 μ m and suppress, and inject electrolyte solution so that 18650 cylindrical battery cells to be provided.Electrolyte solution is by the LiPF of dissolving 1mol/L in mixed solvent
6And prepare, this mixed solvent is by preparing with the inferior propyl ester (PC) of the volume ratio mixed carbonic acid of 1:1:1, diethyl carbonate (DEC), ethylene carbonate (EC).
The battery unit evaluating characteristics
1. charge/discharge capacity and formation efficiency
Change into and discharge and recharge following carrying out: battery unit is charged to 4.4V with 0.2C, with 0.2C it is discharged to 2.75V again.
Table 6
| Negative pole | Charging capacity (mAh) | Discharge capacity (mAh) | Formation efficiency (%) |
| Comparative Examples 1 | 4356.6 | 3014.8 | 69.2 |
| Embodiment 21 | 4374.3 | 3182.5 | 72.8 |
| |
4369.9 | 3200.2 | 73.2 |
| Embodiment 9 | 4347.8 | 3209.0 | 73.8 |
| |
4361.0 | 3209.0 | 73.6 |
As shown in table 6, have better initial charge/discharge capacity and formation efficiency according to the negative pole that comprises interpenetrating networks of embodiment 3,9,15 and 21 than the negative pole of Comparative Examples 1.
Electrode expansion rate that embodiment 3,9,15 and 21 negative pole are also measured.They all have similar electrode expansion rate.Therefore, according to the negative pole that comprises cross-linked network of the present invention because the flexible and elasticity that this cross-linked network and/or fluorinated adhesive are given and do not have the electrode expansion.
2. cycle life characteristics evaluation
To embodiment 3-6,9,10,15 and 21 and the negative pole of Comparative Examples 1,5-8 and 9 estimated cycle life characteristics.Cycle life evaluation is carried out under 4.3V～2.75V scope and the current condition (once discharging and recharging) in 0.8C～1C scope.Discharge capacitance is used for the evaluation cycle life characteristic.Discharge capacitance is calculated with the percentage of the relative initial capacity of capacity behind the 100th cycle charge-discharge.The result is illustrated in the table 7.
Table 7
| ? | 100 thCapability retention (%) |
| |
71 |
| |
75 |
| |
75 |
| |
70 |
| Embodiment 9 | 80 |
| |
80 |
| |
72 |
| Comparative Examples 1 | 60 |
| Comparative Examples 5 | 23 |
| Embodiment 21 | 60 |
| Comparative Examples 6 | 5 |
| Comparative Examples 7 | 15 |
| Comparative Examples 8 | 17 |
| Comparative Examples 9 | 10 |
With reference to table 7, comprise that the battery unit of negative pole of the present invention has the cycle life characteristics of improvement.
Electrode performance is estimated
1. adhesion strength evaluation
To embodiment 3-9,21 and 22 and the negative pole of Comparative Examples 1,5,6,7 and 8 estimated adhesion strength.
Adhesion strength is following to be measured: the negative pole of embodiment and Comparative Examples is pasted the versatile material test machine (can obtain from INSTRON Co.Ltd.) with single cylinder, peel off current collector layers with 50.0mm/min speed, 90 ° of angles then.Measure the adhesion strength of vacuum heat front and back.The result is illustrated in the table 8.
Table 8
Embodiment 3-9 and 21 negative pole have relative excellent adhesion strength than the negative pole of Comparative Examples 7 and 9.The negative pole of embodiment 22 adhesion strength after heat treatment reduces, but it has high starting efficiency.The negative pole of Comparative Examples 1 has high adhesion strength, but starting efficiency is low.The negative pole of Comparative Examples 5 has high adhesion strength, but have can not be measured low starting efficiency.
2. the flexible evaluation of electrode
In order to estimate the flexible interpolation of whether depending on terpolymer (being fluorinated or rubber polymer) of electrode, it is flexible that the negative pole of embodiment 3,9,15,21 and 22 has been estimated electrode.The negative pole of each embodiment is wound into prismatic battery and the damaged situation of visualization.The result is illustrated in the table 9.The damaged result who observes based on embodiment 3 be divided into height, in or low.
Table 9
| Embodiment 21 | Embodiment 22 | |
Embodiment 9 | |
| In | In | High | High | High |
As shown in table 9, embodiment 3,9,15,21 and 22 negative pole have and can be used in the flexible fully of high capacity rechargeable cell.Particularly, comprise that the negative pole (embodiment 3,9 and 15) of fluorinated or rubber polymer has the flexible of excellence, can be used in rechargeable battery cells with high power capacity.
Though with reference to specific illustrative embodiments the present invention is specifically described, those skilled in the art should be understood that and can carry out various changes on form and composition under the situation without departing from the spirit and scope of the present invention.
Claims (17)
1. lithium rechargeable battery negative pole, comprise: collector and the anode active material layer on described collector, described anode active material layer comprises the negative active core-shell material in interpenetrating networks and the described interpenetrating networks, and described interpenetrating networks carry out crosslinked formation by first polymer that will have hydroxyl or amido and second polymer with carboxyl;
The wherein said crosslinked heat treatment first time by under the temperature of 80～120 ℃ of scopes, and carry out in the heat treatment second time under the temperature of 130～200 ℃ of scopes, under vacuum; And
Described first polymer comprises by one in the repetitive of following structural formula 1～3 expression:
Structural formula 1
R wherein
1And R
4Be C1～C4 alkylidene or alkylene oxide group independently respectively;
R
2And R
3Be independently-(CRR ') respectively
n-, wherein R and R ' difference are hydrogen or C1～C5 alkyl independently, n is 1～4 integer;
X and Y are independently selected from alkali metal respectively;
Structural formula 2
R wherein
5～R
7And R
10Be hydrogen or C1～C5 alkyl independently respectively;
R
8For-(CRR ')
n-, wherein R and R ' difference are hydrogen or C1～C5 alkyl independently, n is 0～4 integer;
R
9And R
11Be independently selected from respectively by hydrogen, C1～C5 alkyl and-(CRR ')
n" in the group that constitutes, wherein " be hydrogen or C1～C5 alkyl independently respectively, n is 1～4 integer to OR for R, R ' and R;
R
12For-OCOZ, wherein Z is an alkali metal;
M is in 0.1～1 scope;
Structural formula 3
R wherein
13, R
15And R
17～R
22Be independently-(CRR ') respectively
n-, R and R ' difference are hydrogen or C1～C5 alkyl independently here, n is 1～4 integer;
R
14And R
16Be independently-[(CRR ') respectively
p-(NH)]
q-, wherein R and R ' difference are hydrogen or C1～C5 alkyl independently, and p is 1～4 integer, and q is 1 or 2 integer;
Described second polymer comprises the polymer of the repetitive with following structural formula 4:
Structural formula 4
R wherein
23～R
25And R
28Be hydrogen or C1～C5 alkyl independently respectively;
R
26For-(CRR ')
n-, wherein R and R ' difference are hydrogen or C1～C5 alkyl independently, n is 0～4 integer;
R
27And R
29Be independently selected from respectively by hydrogen, C1～C5 alkyl and-(CRR ')
n" in the group that constitutes, wherein " be hydrogen or C1～C5 alkyl independently respectively, n is 1～4 integer to OR for R, R ' and R;
R
30For-OCOZ, wherein Z is an alkali metal; And
0＜z≤1。
2. negative pole according to claim 1, wherein said interpenetrating networks form by further crosslinked terpolymer, and described terpolymer is rubber-like or fluorinated polymer;
The terpolymer of wherein said rubber polymer is selected from by in butadiene-styrene rubber (SBR), acrylonitrile-butadiene rubber (NBR), methyl methacrylate butadiene rubber, chloroprene rubber, carboxy-modified butadiene-styrene rubber, modified polyorganosiloxanes base polymer and their group that constitutes; And
The terpolymer of described fluorinated polymer is selected from by in the copolymer of Kynoar (PVDF), vinylidene chloride and hexafluoropropylene and their group that constitutes.
3. negative pole according to claim 1, electrochemical reaction does not take place in wherein said interpenetrating networks.
4. negative pole according to claim 1, the hot strength of wherein said interpenetrating networks are 40MPa or littler.
5. negative pole according to claim 1, wherein in immersing electrolyte solution during 12 hours fore-and-aft surveys, described interpenetrating networks have 5% or littler solvent resistance.
6. negative pole according to claim 1, wherein said interpenetrating networks comprise first and second polymer of mol ratio 95: 5～20: 80 scopes.
7. negative pole according to claim 2, wherein the mol ratio of first and second polymer and terpolymer was 95: 5～60: 40 scopes.
8. negative pole according to claim 1, wherein first polymer is selected from the group that copolymer, polymine and their mixture by copolymer, vinyl alcohol and the butyl methacrylate of copolymer, vinyl alcohol and the butyl acrylate of copolymer, vinyl alcohol and the ethyl acrylate of copolymer, vinyl alcohol and the EMA of copolymer, vinyl alcohol and the methyl acrylate of copolymer, vinyl alcohol and cinnamic copolymer, vinyl alcohol and the methyl methacrylate of carboxymethyl cellulose, polyvinyl alcohol, vinyl alcohol and vinylacetate constitute.
9. negative pole according to claim 1, wherein the weight average molecular weight of first polymer (Mw) is 1000～1,000,000 scope.
10. negative pole according to claim 1, wherein second polymer is selected from the group by the copolymer of copolymer, (methyl) acrylic acid and (methyl) butyl acrylate of poly-(methyl) acrylic acid, (methyl) acrylic acid and (methyl) ethyl acrylate and their mixture formation.
11. negative pole according to claim 1, wherein the weight average molecular weight of second polymer is 1000～1,000,000 scope.
12. negative pole according to claim 1, wherein first and second polymer are water-soluble polymer.
13. negative pole according to claim 1, wherein said negative active core-shell material be selected from by the lithium metal, can with lithium form alloy metal material, transition elements oxide, can reversibly mix with lithium conciliate the material, the material that can reversibly form lithium-containing compound that mix, can reversibly embed and group that the material of de-embedding lithium ion constitutes in.
14. negative pole according to claim 1, wherein with respect to the total weight of active material layer, the amount of negative active core-shell material is in 80～99wt% scope.
15. negative pole according to claim 1, wherein said anode active material layer with respect to the adhesion strength of collector in 0.05N/mm～0.2N/mm scope.
16. negative pole according to claim 1, after wherein said negative pole was dipped into electrolyte solution, the thickness swelling of described negative pole was 40% or littler.
17. a lithium rechargeable battery comprises:
Any described negative pole in the claim 1～16;
Anodal; And
Electrolyte.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070122158 | 2007-11-28 | ||
| KR1020070122158A KR101041126B1 (en) | 2007-11-28 | 2007-11-28 | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same |
| KR10-2007-0122158 | 2007-11-28 | ||
| KR1020080035758A KR20090110133A (en) | 2008-04-17 | 2008-04-17 | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery comprising the same |
| KR10-2008-0035758 | 2008-04-17 | ||
| KR1020080035758 | 2008-04-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101447561A CN101447561A (en) | 2009-06-03 |
| CN101447561B true CN101447561B (en) | 2011-08-17 |
Family
ID=40743064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101807258A Active CN101447561B (en) | 2007-11-28 | 2008-11-28 | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101041126B1 (en) |
| CN (1) | CN101447561B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022126138A1 (en) * | 2020-12-11 | 2022-06-16 | Global Graphene Group, Inc. | Elastic crosslinked network of polymer-encapsulated anode particles for lithium batteries and method of manufacturing |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5879673B2 (en) * | 2009-09-03 | 2016-03-08 | ソニー株式会社 | Method for producing negative electrode for non-aqueous electrolyte secondary battery |
| JP5493617B2 (en) * | 2009-09-14 | 2014-05-14 | 信越化学工業株式会社 | Anode for non-aqueous electrolyte secondary battery and lithium ion secondary battery |
| WO2011101987A1 (en) * | 2010-02-22 | 2011-08-25 | トヨタ自動車株式会社 | Lithium ion secondary battery and production method for same |
| DE112011102864T8 (en) * | 2010-08-31 | 2013-08-29 | Toyota Jidosha Kabushiki Kaisha | Anode material, lithium secondary battery and method of making anode material |
| KR101223624B1 (en) * | 2010-09-17 | 2013-01-17 | 삼성에스디아이 주식회사 | Binder composition for rechargeable lithium battery, composition for forming negative active material layer and rechargeable lithium battery including the same |
| JPWO2012063745A1 (en) * | 2010-11-08 | 2014-05-12 | 独立行政法人産業技術総合研究所 | Negative electrode material for electric storage device and negative electrode for electric storage device using the same |
| CN102290577B (en) * | 2011-07-25 | 2016-03-23 | 东莞新能源科技有限公司 | A kind of negative pole of lithium ion battery |
| EP2573845B1 (en) * | 2011-09-26 | 2018-10-31 | VARTA Micro Innovation GmbH | Structural active material for battery electrodes |
| FR2985598B1 (en) * | 2012-01-06 | 2016-02-05 | Hutchinson | CARBON COMPOSITION FOR SUPERCONDENSER CELL ELECTRODE, ELECTRODE, METHOD FOR MANUFACTURING SAME, AND CELL INCORPORATING SAME. |
| KR20140106292A (en) | 2013-02-26 | 2014-09-03 | 삼성에스디아이 주식회사 | Anode for lithium secondary battery and lithium secondary battery using the same |
| CN103456928B (en) * | 2013-09-02 | 2016-10-26 | 东莞新能源科技有限公司 | composite anode material for lithium ion battery and preparation method thereof |
| CN103579578B (en) * | 2013-11-14 | 2016-03-02 | 宁德新能源科技有限公司 | Lithium ion battery and cathode pole piece thereof |
| KR102295365B1 (en) * | 2014-12-31 | 2021-08-31 | 삼성전자주식회사 | Composite anode active material, preparing method thereof, anode and lithium secondary battery comprising the same |
| KR102475886B1 (en) * | 2015-06-25 | 2022-12-08 | 삼성전자주식회사 | Negative electrode for lithium metal battery and lithium metal battery including the same |
| KR102018270B1 (en) * | 2015-08-27 | 2019-10-21 | 주식회사 엘지화학 | Negative Electrode Having Cured Binder for Secondary Battery and Lithium Secondary Battery Comprising the Same |
| WO2017059117A1 (en) * | 2015-09-29 | 2017-04-06 | A123 Systems, LLC | High capacity anode electrodes with mixed binders for energy storage devices |
| KR102058113B1 (en) * | 2015-11-23 | 2019-12-23 | 주식회사 엘지화학 | Electrode with Improved Adhesion Property for Lithium Secondary Battery and Preparing Method therof |
| CN106876656B (en) * | 2015-12-14 | 2020-01-14 | 微宏动力系统（湖州）有限公司 | Preparation method of negative electrode slurry and negative electrode slurry |
| FR3048821B1 (en) * | 2016-03-08 | 2021-12-17 | Commissariat Energie Atomique | INK INCLUDING A MIXTURE OF POLYACRYLIC ACIDS FOR THE REALIZATION OF A LITHIUM-ION BATTERY ELECTRODE, AND ELECTRODE OBTAINED WITH SUCH AN INK |
| JP6610407B2 (en) * | 2016-04-21 | 2019-11-27 | 株式会社豊田自動織機 | Polymer compound, intermediate composition, negative electrode, power storage device, and method for producing polymer compound |
| EP3514870A4 (en) * | 2016-09-16 | 2020-06-17 | Murata Manufacturing Co., Ltd. | Lithium ion secondary battery negative electrode, lithium ion secondary battery, battery pack, electric vehicle, power storage system, electric tool, and electronic device |
| KR102448299B1 (en) * | 2017-07-03 | 2022-09-28 | 삼성에스디아이 주식회사 | Anode and and lithium battery comprising anode |
| KR102473534B1 (en) * | 2017-09-26 | 2022-12-05 | 삼성전자주식회사 | Negative active material, lithium secondary battery including the material, and method for manufacturing the material |
| CN108878886B (en) * | 2018-07-10 | 2020-12-15 | 东莞市迈科新能源有限公司 | Thick battery pole piece and water-based composite binder thereof |
| JP7461101B2 (en) * | 2018-08-03 | 2024-04-03 | 株式会社Ａｅｓｃジャパン | Lithium ion secondary battery |
| KR102119311B1 (en) * | 2018-08-08 | 2020-06-08 | 주식회사 피엔에스테크놀로지 | Binder composition for lithium secondary battery |
| CN112993252B (en) * | 2019-12-17 | 2022-08-09 | 比亚迪股份有限公司 | Cross-linkable binder composition for negative electrode, negative electrode active material slurry, negative electrode preparation method and lithium ion battery |
| CN113675374B (en) * | 2020-05-15 | 2023-08-08 | 比亚迪股份有限公司 | Negative electrode, preparation method thereof and lithium ion battery |
| WO2022097833A1 (en) * | 2020-11-03 | 2022-05-12 | (주)뉴테크엘아이비 | Polymer binder suitable for silicon-based and carbon-based negative electrode material for lithium secondary battery and method for manufacturing same |
| CN112952094A (en) * | 2021-01-26 | 2021-06-11 | 宁德新能源科技有限公司 | Lithium ion battery and electronic device |
| US20220246915A1 (en) * | 2021-02-04 | 2022-08-04 | Global Graphene Group, Inc. | Thermally stable elastic polymer-encapsulated anode particles for lithium batteries and method of manufacturing |
| WO2023123480A1 (en) * | 2021-12-31 | 2023-07-06 | 东莞新能源科技有限公司 | Binder and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5714282A (en) * | 1995-05-23 | 1998-02-03 | Tagawa; Kazuo | Coating paste and a nonaqueous electrode for a secondary battery |
| CN1543005A (en) * | 2003-04-28 | 2004-11-03 | 三星Sdi株式会社 | Electrolyte for a lithium battery and a lithium battery comprising the same |
| US6881517B1 (en) * | 1999-09-03 | 2005-04-19 | Zeon Corporation | Binder for electrode for lithium ion secondary battery, and utilization thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08321298A (en) * | 1995-05-23 | 1996-12-03 | Kazuo Tagawa | Paste for applying to electrode and non-aqueous type secondary battery electrode |
| KR100497251B1 (en) * | 2003-08-20 | 2005-06-23 | 삼성에스디아이 주식회사 | Protective composition for negative electrode of lithium sulfur battery and lithium sulfur battery fabricated by using same |
| KR100542213B1 (en) * | 2003-10-31 | 2006-01-10 | 삼성에스디아이 주식회사 | Negative electrode of lithium metal battery and lithium metal battery comprisng same |
| DE602006014138D1 (en) * | 2005-04-19 | 2010-06-17 | Korea Res Inst Chem Tech | SAFETY IMPROVED ELECTRODE THROUGH THE INTRODUCTION OF NETWORKABLE POLYMER AND ELECTROCHEMICAL EQUIPMENT THEREWITH |
-
2007
- 2007-11-28 KR KR1020070122158A patent/KR101041126B1/en active IP Right Grant
-
2008
- 2008-11-28 CN CN2008101807258A patent/CN101447561B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5714282A (en) * | 1995-05-23 | 1998-02-03 | Tagawa; Kazuo | Coating paste and a nonaqueous electrode for a secondary battery |
| US6881517B1 (en) * | 1999-09-03 | 2005-04-19 | Zeon Corporation | Binder for electrode for lithium ion secondary battery, and utilization thereof |
| CN1543005A (en) * | 2003-04-28 | 2004-11-03 | 三星Sdi株式会社 | Electrolyte for a lithium battery and a lithium battery comprising the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022126138A1 (en) * | 2020-12-11 | 2022-06-16 | Global Graphene Group, Inc. | Elastic crosslinked network of polymer-encapsulated anode particles for lithium batteries and method of manufacturing |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20090055307A (en) | 2009-06-02 |
| KR101041126B1 (en) | 2011-06-13 |
| CN101447561A (en) | 2009-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101447561B (en) | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including the same | |
| US7931984B2 (en) | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including the same | |
| CN101447562B (en) | Negative electrodes for rechargeable lithium batteries, and rechargeable lithium batteries including the same | |
| CN101388475B (en) | Rechargeable lithium battery | |
| CN101192663B (en) | An electrode for a rechargeable lithium battery and a rechargeable lithium battery fabricated therefrom | |
| CN101404330B (en) | Negative active material for rechargeable lithium battery, and negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same | |
| CN102412401A (en) | Binder composition for rechargeable lithium battery, and electrode and rechargeable lithium battery including the same | |
| CN109937499A (en) | Positive electrode for lithium secondary battery and the lithium secondary battery including it | |
| CN101615692A (en) | Lithium rechargeable battery | |
| KR20090110133A (en) | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery comprising the same | |
| CN101188294A (en) | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| CN111312989B (en) | Electrode for rechargeable lithium battery and rechargeable lithium battery comprising the same | |
| CN103887562A (en) | Electrolyte additive and electrolyte including same and lithium rechargeble battery including electrolyte | |
| CN110504420A (en) | Negative electrode active material and lithium rechargeable battery including it | |
| KR20150116330A (en) | Rechargeable lithium battery | |
| KR101256065B1 (en) | Positive electrode for rechargeable lithium battery and rechargeable lithium battery including same | |
| KR20170134049A (en) | Positive electrode for rechargeable lithium battery and rechargeable lithium battery including same | |
| KR101711987B1 (en) | Positive active material for lithium secondary battery and lithium secondary battery | |
| CN104282943B (en) | Additive and electrolyte and lithium secondary battery for electrolyte | |
| KR20190134021A (en) | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same | |
| KR20160054315A (en) | Electrode for rechargeable lithium battery and rechargeable lithium battery including the same | |
| KR101702983B1 (en) | Positive electrode for lithium secondary battery and lithium secondary battery | |
| CN110350244B (en) | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same | |
| CN110380110A (en) | Electrode assembly and rechargeable battery including the electrode assembly | |
| KR20190132031A (en) | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |