CN101783401A - Cathode and Li-ion battery comprising same - Google Patents
Cathode and Li-ion battery comprising same Download PDFInfo
- Publication number
- CN101783401A CN101783401A CN200910001585A CN200910001585A CN101783401A CN 101783401 A CN101783401 A CN 101783401A CN 200910001585 A CN200910001585 A CN 200910001585A CN 200910001585 A CN200910001585 A CN 200910001585A CN 101783401 A CN101783401 A CN 101783401A
- Authority
- CN
- China
- Prior art keywords
- negative pole
- low crystalline
- crystalline carbon
- negative
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a cathode, which comprises current collector and a cathode material coating loaded on the current collector, wherein the cathode material comprises cathodal active substance and binder; the cathodal active substance is low crystalline carbon and lithium metal nitride; the lithium metal nitride is coated on the surface of the low crystalline carbon and/or the cathode material coating comprising at least two layers, the low crystalline carbon is arranged in an inner layer close to the current collector, and the lithium metal nitride is arranged in an outer layer; and the inner layer is arranged between the outer layer and the current collector. The invention also provides a Li-ion battery comprising the cathode in the invention. By using the cathode provided by the invention, the phenomenon of lithium de-intercalation lag is overcome, the discharge-charge properties of the battery are remarkably improved, and the battery safety is enhanced.
Description
Technical field
The present invention relates to a kind of negative pole and the lithium rechargeable battery that comprises this negative pole.
Background technology
At present, the application of lithium ion battery more and more widely from traditional mobile phone development to portable dam, notebook, has nowadays developed on pure electric automobile (EV) and the hybrid vehicle (HEV) especially.The performance that increases also lithium ion battery itself of application has proposed more requirement, especially EV and HEV field, requirement to useful life, rate charge-discharge performance and the security performance of battery is also more harsh, will have better chemical property so make the material of lithium ion battery.Now, the lithium ion battery negative material of industrial extensive use is a Delanium, and the capacity of its 372mAh/g is low excessively, and structural instability, and is too high to the electrolyte susceptibility, can't satisfy the requirement of lithium ion battery.Thereby researchers begin to seek other new alternative negative material.
Low crystalline carbon material has caused people's attention because of its lower cost and metastable doff lithium structure.Low crystalline carbon material heat treatment temperature is lower, generally below 2300 ℃, comprises hard carbon, soft carbon etc.Be generally disordered structure, degree of crystallinity is low, and crystallite dimension is little, and interplanar distance is bigger, structural change is little in the charge and discharge process, good with the compatibility of electrolyte, the reversible capacity height, but irreversible capacity is also very big, the first charge-discharge coulombic efficiency is low, but also have the more serious problem of taking off lithium hysteresis (insert the lithium current potential and approach 0V, take off the lithium current potential and approach 1V), so the application in actual battery is very restricted.For this material, more to the research that how to improve its reversible capacity.
Li
3N also is a kind of more promising negative material, its ionic conductivity (10
-3Scm
-1) very high, far above graphite (10
-9Scm
-1), but its decomposition voltage is lower, is about 0.44V, is not suitable for as electrode material.It and transition metal such as Co, Ni, Cu, Fe, Mn, Mg etc. are obtained metal lithium nitride Li after having an effect
3-xM
xN (0≤x≤0.7).Li
3-xM
xN has good chemical stability and electronics, ionic conductivity, and density and graphite are suitable, and the reversible embedding of taking off can take place the lithium in the self structure, and charge/discharge capacity is between 200-1200mAh/g.But it is higher to insert the lithium current potential, between 0.6-1.2V, it is applied to the working voltage that negative material can reduce battery separately.
For this reason, CN1877888A discloses a kind of hard carbon-metal lithium nitride composite cathode materials and preparation method thereof, described hard carbon-metal lithium nitride composite cathode materials contains hard carbon and metal lithium nitride, and its mass ratio satisfies: the superfluous first discharge capacity of metal lithium nitride can compensate the irreversible capacity first of hard carbon.The preparation method of described hard carbon-metal lithium nitride composite cathode materials comprises hard carbon, metal lithium nitride under inert gas atmosphere, fully be mixed with hard carbon-metal lithium nitride composite cathode materials at normal temperatures, the method for described mixing is the conventional method that mixes or ball-milling method.The hard carbon-metal lithium nitride composite cathode materials of method acquisition has reduced the irreversible capacity first of negative material thus, coulombic efficiency, electro-chemical activity etc. have been improved, but can't solve the lithium hysteresis problem of taking off in the hard carbon material doff lithium process, cause battery can't give play to high energy density.
Summary of the invention
The objective of the invention is to exist and break away from the serious problem of hysteresis in order to overcome in the prior art negative material, provide a kind of reversible capacity higher, hardly can produce take off that lithium lags behind, the negative pole that high rate charge-discharge performance and security performance are superior and the lithium rechargeable battery that comprises this negative pole.
The invention provides a kind of negative pole, this negative pole comprises collector and the negative material coating that loads on this collector, described negative material contains negative electrode active material and adhesive, described negative electrode active material is low crystalline carbon and metal lithium nitride, wherein, surface and/or described negative material coating that described metal lithium nitride is coated on described low crystalline carbon comprise two-layer at least, wherein said low crystalline carbon is arranged in the internal layer near collector, described metal lithium nitride is arranged in skin, and described internal layer is between skin and collector.
The present invention also provides a kind of lithium rechargeable battery, this battery comprises battery container, electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery container, described electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, wherein, described negative pole is a negative pole provided by the invention.
Negative pole provided by the invention and lithium rechargeable battery, comprise two-layer at least because described metal lithium nitride is coated on the surface and/or the described negative material coating of described low crystalline carbon, wherein said low crystalline carbon is arranged in the internal layer near collector, described metal lithium nitride is arranged in skin, described internal layer is between skin and collector, solved effectively and taken off the phenomenon that lithium lags behind, simultaneously, adopt negative pole provided by the present invention, reversible specific capacity and efficiency for charge-discharge are significantly improved, for example the negative pole reversible specific capacity of embodiment 1 is 542mAh/g, efficiency for charge-discharge is 87.6%, and the negative pole reversible specific capacity of Comparative Examples 1 is 500mAh/g, and efficiency for charge-discharge is 82.3%.
Description of drawings
Fig. 1 is the charging curve of embodiment 1-6 button cell;
Fig. 2 is the charging curve of Comparative Examples 1-5 button cell.
Embodiment
The invention provides a kind of negative pole, this negative pole comprises collector and the negative material coating that loads on this collector, described negative material contains negative electrode active material and adhesive, described negative electrode active material is low crystalline carbon and metal lithium nitride, wherein, surface and/or described negative material coating that described metal lithium nitride is coated on described low crystalline carbon comprise two-layer at least, wherein said low crystalline carbon is arranged in the internal layer near collector, described metal lithium nitride is arranged in skin, and described internal layer is between skin and collector.
Described collector can be the conventional various materials as the lithium ion battery negative collector that use in this area, for example, can adopt in nickel, copper and the stainless steel one or more, wherein preferably be easy to be processed into film and low-cost Copper Foil, the rolled copper foil that rolling process makes, the electrolytic copper foil that electrolysis obtains are arranged in the Copper Foil, all can be used as negative current collector.
Described internal layer contains low crystalline carbon and adhesive, and the weight ratio of described low crystalline carbon and adhesive can be 100: 0.3-100: 15; Described skin contains metal lithium nitride and adhesive, and the weight ratio of described metal lithium nitride and adhesive can be 100: 0.3-100: 15.In addition, described internal layer also can also contain metal lithium nitride, as long as described low crystalline carbon is all covered and directly do not contact with air by metal lithium nitride.
According to negative pole provided by the present invention, the consumption of described low crystalline carbon and metal lithium nitride can be selected in a big way, as long as can guarantee that described low crystalline carbon is all covered and directly do not contact with air by metal lithium nitride, under the preferable case, the weight ratio of described low crystalline carbon and metal lithium nitride is greater than 1, and more preferably 100: 30-100: 3.
Described low crystalline carbon and metal lithium nitride can be conventional low crystalline carbon and the metal lithium nitrides that uses in this area, and for example the d002 value of described low crystalline carbon can be the 0.34-0.40 nanometer, is preferably the 0.345-0.385 nanometer; The Lc value of described low crystalline carbon is preferably the 0.8-40 nanometer less than 60 nanometers; The La value of described low crystalline carbon is less than 50 nanometers, be preferably the 0.5-20 nanometer, wherein, d002 is the distance between low crystalline carbon 002 crystal face among the XRD, the thickness that Lc piles up along perpendicular c direction of principal axis for low crystalline carbon 002 crystal face, La is for hanging down the crystalline carbon crystal along the axial mean size of a.Satisfy above-mentioned condition described low crystalline carbon can for various by heat treatment temperature below 2300 ℃, preferred 600-1400 ℃ of low crystalline carbon that obtains down.
Concrete, described low crystalline carbon can be various hard carbons and/or soft carbon, described hard carbon can be one or more in resin carbon, organic polymer RESEARCH OF PYROCARBON, carbon black, the non-crystalline semiconductor material polyacene difficult graphited hard carbons such as (PAS), and described soft carbon can be one or more in the easy graphited soft carbon such as petroleum coke, needle coke, carbonaceous mesophase spherules (MCMB), mesocarbon fiber (MCF), nano carbon black.The definition that hard carbon described herein and soft carbon are continued to use this area routine, promptly more difficult graphited carbonaceous material is called hard carbon, and easier graphited material is called soft carbon.Described low crystalline carbon also can be various be that the material that doping vario-property makes is carried out on the basis with low crystalline carbon, as mix phosphorus pitch coke etc.Wherein, described resin carbon specifically can be one or more solid products that obtain 2300 ℃ of preferred 600-1400 ℃ of following heat treatments among phenolic resins, epoxy resin, the glycan alcohol PFA-C, and described organic polymer RESEARCH OF PYROCARBON specifically can be one or more solid products that obtain 2300 ℃ of preferred 600-1400 ℃ of following heat treatments in glycan alcohol RESEARCH OF PYROCARBON (PFA), benzene carbon (BC), acetylene black (AB), the polyvinyl chloride RESEARCH OF PYROCARBON (PVCC).The particle diameter of described low crystalline carbon is preferably the 0.8-20 micron.Above-mentioned low crystalline carbon can be commercially available, and also can prepare by means commonly known in the art.
Described metal lithium nitride can be Li
3-xM
xN, wherein, x is 0≤x≤0.7; M can be at least a among Co, Mn, Ni, Cu, Al, Mg, Ga, Fe, Ti, V, Zn, Sn and the Cr, is preferably among Mg, Fe, Co, Cu, the Ni at least aly, can further improve the reversible capacity of negative pole like this, thereby improve the energy density of battery.Doped metal nitride more preferably is as Cu and Ni or Co and Fe or Co and Mg.The particle diameter of described metal lithium nitride is preferably the 0.05-30 micron.Above-mentioned metal lithium nitride can be commercially available, and also can prepare by means commonly known in the art.
Because the present invention relates generally to the kind of anticathode active material and improves, there is no particular limitation for the consumption of anticathode active material and the kind of adhesive and consumption, under the preferable case, in the described negative pole, the content of described binding agent is the 0.01-20 weight % of negative electrode active material weight, is preferably 1-10 weight %.Binding agent in the described internal layer and the adhesive in the skin have no particular limits, can be the same or different, for example can adopt sodium carboxymethylcellulose, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene, polypropylene, ethylene/propylene/diene hydrocarbon terpolymer (EPDM, ethylene propylene diene rubber), in sulfonated epdm, styrene/butadiene rubbers (SBR) and the fluorubber one or more, preferred PVDF.
In addition, the thickness of negative material coating can be selected in a big way according to the charge/discharge capacity of battery in the negative pole of the present invention, and there is no particular limitation, is preferably the 0.100-0.150 millimeter.
Except metal lithium nitride and low crystalline carbon, the negative material of negative pole provided by the invention can also contain conductive agent, described conductive agent can be the conventional various conductive agents that use in this area, for example can be in conductive black, copper powder, the nickel powder one or more.There is no particular limitation to the content of conductive agent, can be preferably 1-20 weight % for the 0-50 weight % of negative electrode active material.
According to negative pole provided by the present invention, can be by methods such as coating or secondary coatings, also can comprise two-layer at least by on the basis that coats, carrying out surface and/or described negative material coating that secondary or the coating more than the secondary make metal lithium nitride be coated on described low crystalline carbon again, wherein said low crystalline carbon is arranged in the internal layer near collector, described metal lithium nitride is arranged in skin, and described internal layer is between skin and collector.
The method of described coating refers to coat metal lithium nitride on the surface of low crystalline carbon active material; Described secondary applies and refers to apply the slurry that contains the metal lithium nitride active material on the pole piece that contains low crystalline carbon active material, is made into negative pole.
A preferred embodiment of the invention, the preparation method of described negative pole comprises the surface that metal lithium nitride is coated to low crystalline carbon, obtain the low crystalline carbon that metal lithium nitride coats, the low crystalline carbon that this metal lithium nitride is coated mixes with the conductive agent that binder solution and selectivity contain then, obtain cathode size, this cathode size is loaded on the negative current collector, dry out solvent, roll-in, promptly get negative plate after cutting.The method that metal lithium nitride is coated to the surface of low crystalline carbon can be in TVD method, physical vaporous deposition, the vapour deposition method one or more.The consumption of metal lithium nitride is coated low crystalline carbon fully, is satisfying under the situation of above-mentioned condition, and the weight ratio of further preferred described low crystalline carbon and metal lithium nitride is greater than 1, and more preferably 100: 30-100: 3.Can judge whether low crystalline carbon is coated by metal lithium nitride fully in the low crystalline carbon that metal lithium nitride coats, if coat fully, then granular boundary is fuzzy in the SEM collection of illustrative plates, and floccule is arranged by SEM (transmission electron microscope); Otherwise granular boundary is clear.Can adopt also whether low crystalline carbon is coated by metal lithium nitride fully in the low crystalline carbon that EDS (Energy DispersiveSpectrometer) judges that metal lithium nitride coats, if do not occur the peak of carbon in the EDS test result, then coat fully, otherwise coating is incomplete.
According to another embodiment of the invention, the preparation method of described negative pole comprises low crystalline carbon and metal lithium nitride is mixed with the conductive agent that binder solution and selectivity contain respectively, obtain first cathode size and second cathode size, then this first cathode size is loaded on the negative current collector, carry out primary coating, again second cathode size is loaded on the coating that is formed by first cathode size after the oven dry, carrying out secondary applies, the coating procedure of above-mentioned load first cathode size and second cathode size can repeat repeatedly, in other words away from the outmost coating of collector is metal lithium nitride coating away from the outmost coating of collector for the coating that does not contain low crystalline carbon as long as guarantee.The coating total amount of first cathode size and second cathode size makes the weight ratio of described low crystalline carbon and metal lithium nitride greater than 1, and more preferably 100: 30-100: 3.
Used solvent can be the conventional all kinds of solvents that uses in this area in the above-mentioned preparation cathode size, as long as the adhesive dissolving can be formed binder solution, and do not get final product, for example can be selected from aqueous solvent or organic solvent with low crystalline carbon and metal lithium nitride reaction.As aqueous solvent, make water usually, but also can add additive therein such as cyclic amides such as alcohols such as ethanol, N-methyl pyrrolidones.As organic solvent, usually can select N-methyl pyrrolidone (NMP), N for use, dinethylformamide, N, one or more in N-dimethylacetylamide, anisole, toluene, dimethylbenzene, butanols, the cyclohexanol, cyclic amides such as wherein preferred N-methyl pyrrolidone.These materials may be used alone, two or more kinds can also be used.Consumption to solvent is not particularly limited, and applies the operability requirement as long as can form cathode size and satisfy.For example, the consumption of described solvent can be the 30-75 weight % of low crystalline carbon and metal lithium nitride total weight, preferred 40-55 weight %.
The condition of described drying and roll-in has no particular limits, for example can set dry just/temperature of cathode pole piece is 60-120 ℃, preferred 80-110 ℃, be 0.5-5 hour drying time.
The present invention also provides a kind of lithium rechargeable battery, this battery comprises battery container, electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery container, described electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, wherein, described negative pole is a negative pole provided by the invention.
According to lithium ion battery provided by the present invention, described positive pole comprises collector and the positive electrode material layer that is coated on this collector.Described positive electrode material layer includes positive active material and binding agent, also optionally includes conductive agent.
According to lithium ion battery provided by the present invention, as long as but described positive active material has the function of embedding-Tuo lithium, there is not special qualification, can use the transition oxide that contains lithium, as LiFePO
4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F, LiFeO
2Deng, perhaps ternary system Li
1+xL
1-y-zM
yN
zO
2, wherein-and 0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0, L, M, N are at least a in Co, Mn, Ni, Al, Mg, Ga and the 3d transiting group metal elements.
According to lithium ion battery provided by the present invention, described anodal binding agent can be thermoplastic resin or thermosetting resin.For example polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polymer with caoutchouc elasticity comprise ethylene/propylene/diene hydrocarbon terpolymer (EPDM, ethylene propylene diene rubber), sulfonated epdm, styrene/butadiene rubbers (SBR) and fluorubber etc.Use comparatively extensively polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) in the preferred lithium ion battery at present.The content of described binding agent is the 0.1-15 weight % of described positive electrode, is preferably 1-7 weight %.
According to lithium ion battery provided by the present invention, described anodal conductive agent has no particular limits, and for example can adopt in graphite, carbon fiber, carbon black, metal dust and the fiber one or more.The content of described conductive agent is the 0.1-20 weight % of described positive electrode, is preferably 2-10 weight %.
According to lithium ion battery provided by the present invention, described plus plate current-collecting body has no particular limits, and can adopt materials such as aluminium foil, stainless steel foil, nickel foil, preferred aluminium foil.
According to lithium ion battery provided by the present invention, just described/negative material coating can adopt method preparation commonly used at present.For example, positive active material, conductive agent and binding agent be dissolved in according to a certain percentage be mixed into slurries in the solvent, apply these slurries again on the wide cut collector, dry then, roll-in is cut, and obtains the anode pole piece of suitable dimension.
According to lithium rechargeable battery provided by the invention, membrane layer is arranged at and makes it not take place the physics contact between positive pole and the negative pole, preferred ion permeability height, resistance be low, stable and protect the barrier film of fluidity excellence with respect to electrolyte, for example can select polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
According to lithium rechargeable battery provided by the invention, electrolyte can be selected nonaqueous electrolytic solution.Electrolyte lithium salt can be for being selected from lithium hexafluoro phosphate (LiPF in the described nonaqueous electrolytic solution
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
According to lithium rechargeable battery provided by the invention, the preparation method of this battery is as well known to those skilled in the art, in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, add electrolyte, sealing obtains lithium rechargeable battery then.Wherein, the method for sealing, the consumption of electrolyte does not have specific (special) requirements, as long as can satisfy the battery charging and discharging circulation.
Be that example is further described the present invention with the LP053450 battery below.
Embodiment 1
Present embodiment is used to illustrate negative pole provided by the invention and lithium rechargeable battery.
Anodal making: with LiCoO
2, carbon black and PVDF be to be dissolved in N-methyl pyrrolidone at 100: 8: 5 with weight ratio, be coated on the aluminium foil after stirring, 90 ℃ of oven dry down, roll, rolling cut becomes anode pole piece as positive pole, and coating layer thickness is the 0.129-0.134 millimeter, the pole piece size is 480 millimeters * 42.5 millimeters, LiCO
2Content is 5.12 grams.
The making of negative pole: phenolic resin curing is pulverized, be warmed up to 1100 ℃ of pyrogenically prepared amorphous poly acene materials with 0.8 ℃/min, detect discovery by XRD, the d002 value of this amorphous poly acene material is 0.371 nanometer, the La value is 0.875 nanometer, the Lc value is 6.102 nanometers, and average grain diameter is 10.3 microns, and specific area is 2.18 meters squared per gram.Then at 1100 ℃, purity under the dry ammonia atmosphere more than the 99 weight %, pure phase lithium nitride and cobalt powder were deposited on amorphous poly acene material surface by weight 13: 2, form Li
2.6Co
0.4N is shell, the structure of amorphous poly acene material for examining, and makes negative electrode active material m1, Li
2.6Co
0.4N accounts for 10.7 weight % of negative electrode active material m1 total amount.Detect discovery by EDS, amorphous poly acene material is fully by Li
2.6Co
0.4N coats.Is to be dissolved in NMP at 100: 4: 8 m1, conductive carbon black and PVDF with weight ratio, be coated on the Copper Foil after stirring, 90 ℃ of oven dry down, roll, cut into cathode pole piece as negative pole, coating layer thickness is the 0.105-0.109 millimeter, and the pole piece size is 493 millimeters * 44 millimeters, and the content of m1 is 1.61 grams.
With the lithium-ion electric core of the square of polypropylene (PP) membrane coil coiled of above-mentioned positive and negative electrode pole piece and 25 micron thickness and be received in the rectangular cell shell, inject 1 mol LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 1) electrolyte, sealing is made thick 5 millimeters, and is wide 34 millimeters, high 50 millimeters square lithium ion battery.
Comparative Examples 1
Method according to embodiment 1 prepares negative pole and lithium rechargeable battery, and different is, with Li
2.6Co
0.4N and amorphous poly acene material directly mix with weight ratio at 10.7: 89.3, make negative electrode active material m1, Li
2.6Co
0.4N accounts for 10.7 weight % of negative electrode active material m1 total amount.Obtain negative pole and lithium rechargeable battery.
Embodiment 2
Present embodiment is used to illustrate negative pole provided by the invention and lithium rechargeable battery.
According to the method identical with embodiment 1, different is the making of negative pole.
The making of negative pole: pitch is made MCMB 700 ℃ of pyrolysis carbonization treatment, and its d002 value is 0.347 nanometer, and the La value is 0.927 nanometer, and the Lc value is 1.056 nanometers, and average grain diameter is 25.1 microns, and specific area is 4.29 meters squared per gram.Get Li
2.1Ni
0.9N, its average grain diameter is 0.2 micron, and it is scattered in the alcohol solvent, adds above-mentioned MCMB then, and ultrasonic dispersion 20min continues to stir 30min, filters, and 230 ℃ of oven dry make negative electrode active material m2, Li with 500 ℃ of heat treatments again
2.1Ni
0.9The N ratio is 21.8 weight amount %.Is to be dissolved in NMP at 100: 4: 8 m2, conductive carbon black and PVDF with weight ratio, is coated on the Copper Foil after stirring, and 90 ℃ of oven dry down, rolls, and is made into pole piece one time, and coating layer thickness is the 0.082-0.086 millimeter.Get Li
2.1Ni
0.9N is to be dissolved in NMP at 100: 4: 8 itself and conductive carbon black and PVDF with weight ratio, is coated in after stirring on pole piece, 90 ℃ of oven dry down, roll, cut into cathode pole piece as negative pole, coating layer thickness is the 0.097-0.101 millimeter, and the pole piece size is 493 millimeters * 44 millimeters, Li
2.1Ni
0.9The total content of N and MCMB is 1.45 grams.
Comparative Examples 2
Method according to embodiment 2 prepares negative pole and lithium rechargeable battery, and different is, with Li
2.1Ni
0.9N and MCMB directly mix with weight ratio at 21.8: 78.2, make negative electrode active material m2, Li
2.1Ni
0.9N accounts for 21.8 weight % of negative electrode active material m2 total amount.Obtain negative pole and lithium rechargeable battery.
Embodiment 3
Present embodiment is used to illustrate negative pole provided by the invention and lithium rechargeable battery.
According to the method identical with embodiment 1, different is the making of negative pole.
The making of negative pole: glycan alcohol is made glycan alcohol RESEARCH OF PYROCARBON PFA in pyrolysis carbonization treatment below 800 ℃, and its d002 value is 0.383 nanometer, and the La value is 1.164 nanometers, and the Lc value is 4.723 nanometers, and average grain diameter is 6.75 microns, and specific area is 8.30 meters squared per gram.800 ℃, high-purity N
2Protection adopts the method for inert gas high-temperature heat treatment with Li down
2.3Cu
0.7N (its average grain diameter is less than 500 nanometers) is coated on the PFA surface and makes negative electrode active material m3, Li
2.3Cu
0.7The N ratio is 28.4 weight %.Is to be dissolved in NMP at 100: 4: 8 m3, conductive carbon black and PVDF with weight ratio, be coated on the Copper Foil after stirring, 90 ℃ of oven dry down, roll, cut into cathode pole piece as negative pole, coating layer thickness is the 0.116-0.120 millimeter, and the pole piece size is 493 millimeters * 44 millimeters, and the content of m3 is 1.87 grams.
Comparative Examples 3
Method according to embodiment 3 prepares negative pole and lithium rechargeable battery, and different is, with Li
2.3Cu
0.7N and PFA directly mix with weight ratio at 28.4: 71.6, make negative electrode active material m3, Li
2.3Cu
0.7N accounts for 28.4 weight % of negative electrode active material m3 total amount.Obtain negative pole and lithium rechargeable battery.
Embodiment 4
Present embodiment is used to illustrate negative pole provided by the invention and lithium rechargeable battery.
According to the method identical with embodiment 1, different is the making of negative pole.
The making of negative pole: get the benzene carbon that 900 ℃ of heat treatments make, its d002 value is 0.349 nanometer, and the La value is 7.132 nanometers, and the Lc value is 21.641 nanometers, and average grain diameter is 17.21 microns, and specific area is 2.65 meters squared per gram, with itself and Li
2.6Co
0.35Fe
0.05N (its average grain diameter is 21.2 microns), conductive carbon black and PVDF are 100: 6: 4 with weight ratio: 8 are dissolved among the NMP, are coated on the Copper Foil after stirring, and 90 ℃ of oven dry down, roll, and are made into pole piece one time, and coating layer thickness is the 0.120-0.124 millimeter.Get Li
2.6Co
0.35Fe
0.05N is to be dissolved in NMP at 100: 4: 8 itself and conductive carbon black and PVDF with weight ratio, is coated in after stirring on pole piece, 90 ℃ of oven dry down, roll, cut into cathode pole piece as negative pole, coating layer thickness is the 0.135-0.139 millimeter, and the pole piece size is 493 millimeters * 44 millimeters, Li
2.6Co
0.35Fe
0.05The N ratio is 19.1 weight %, Li
2.6Co
0.35Fe
0.05The total content of N and benzene carbon is 2.26 grams.
Comparative Examples 4
Method according to embodiment 4 prepares negative pole and lithium rechargeable battery, and different is, with Li
2.6Co
0.35Fe
0.05N and benzene carbon directly mix with weight ratio at 19.1: 80.9, make negative electrode active material m4, Li
2.6Co
0.35Fe
0.05N accounts for 19.1 weight % of negative electrode active material m4 total amount.Obtain negative pole and lithium rechargeable battery.
Embodiment 5
Present embodiment is used to illustrate negative pole provided by the invention and lithium rechargeable battery.
According to the method identical with embodiment 1, different is the making of negative pole.
The making of negative pole: get the petroleum coke that 1200 ℃ of heat treatments make, its d002 value is 0.359 nanometer, and the La value is 15.616 nanometers, and the Lc value is 31.250 nanometers, average grain diameter is 5.23 microns, specific area is 13.24 meters squared per gram, is to be dissolved in NMP at 100: 4: 8 itself and conductive carbon black and PVDF with weight ratio, is coated on the Copper Foil after stirring, 90 ℃ of oven dry down, roll, be made into pole piece one time, coating layer thickness is the 0.103-0.107 millimeter.Get Li
2.7Mg
0.3N is to be dissolved in NMP at 100: 4: 8 itself and conductive carbon black and PVDF with weight ratio, is coated in after stirring on pole piece, 90 ℃ of oven dry down, rolls, and cuts into cathode pole piece as negative pole, and coating layer thickness is the 0.121-0.125 millimeter, Li
2.7Mg
0.3The N ratio is 15.4 weight %, and the pole piece size is 493 millimeters * 44 millimeters, Li
2.7Mg
0.3The total content of N and petroleum coke is 1.94 grams.
Comparative Examples 5
Method according to embodiment 5 prepares negative pole and lithium rechargeable battery, and different is, with Li
2.7Mg
0.3N and petroleum coke directly mix with weight ratio at 15.4: 84.6, make negative electrode active material m5, Li
2.7Mg
0.3N accounts for 15.4 weight % of negative electrode active material m5 total amount.Obtain negative pole and lithium rechargeable battery
Embodiment 6
Present embodiment is used to illustrate negative pole provided by the invention and lithium rechargeable battery.
Method according to embodiment 5 prepares negative pole and lithium rechargeable battery, and different is Li
2.7Mg
0.3N adopts the Li of identical weight
2.1Ni
0.9N and Li
2.3Cu
0.7The mixture of N (weight ratio 1: 1) replaces, and obtains negative pole and lithium rechargeable battery.
The negative pole performance test:
1, button cell capacity and curve
To be cut into diameter be 14 millimeters disk to the cathode pole piece that makes with the foregoing description 1-6 and Comparative Examples 1-5 respectively, with these pole pieces is positive pole, with the metal lithium sheet is negative pole assembling button cell, in 0.005-2.5 volt potential region, 0.1C carry out charge-discharge test under the electric current, measure the specific capacity and the efficiency for charge-discharge of each negative pole, and the charging and discharging curve of recording materials, test result such as the table 1 of embodiment 1-6 and Comparative Examples 1-5, the charging curve of embodiment 1-6 and Comparative Examples 1-5 is shown in Fig. 1-2.
Table 1
| Negative pole reversible specific capacity (mAh/g) | Efficiency for charge-discharge | |
| Embodiment 1 | ??542 | ??87.6％ |
| Comparative Examples 1 | ??500 | ??82.3％ |
| Embodiment 2 | ??583 | ??82.4％ |
| Comparative Examples 2 | ??550 | ??78.0％ |
| Embodiment 3 | ??451 | ??81.6％ |
| Comparative Examples 3 | ??416 | ??72.6％ |
| Embodiment 4 | ??374 | ??84.6％ |
| Comparative Examples 4 | ??340 | ??80.6％ |
| Embodiment 5 | ??435 | ??79.5％ |
| Comparative Examples 5 | ??392 | ??68.5％ |
| Embodiment 6 | ??448 | ??80.4％ |
From table 1 data as can be seen, adopt negative pole provided by the present invention, reversible specific capacity and efficiency for charge-discharge are significantly increased.Comparison diagram 1 and Fig. 2 are as can be seen, among Fig. 2 on the charging curve of Comparative Examples the position about 1V one clearly platform is arranged, and almost do not have on the charging curve of the negative pole after employing the present invention improves among Fig. 1, this explanation the present invention can obviously improve low crystalline carbon and take off the problem that lithium lags behind.
The battery behavior test:
1, high-rate performance test
A, heavy-current discharge test
Under the room temperature condition, with battery respectively with the 1C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.2V, shelves 5 minutes; Battery, was shelved 5 minutes to 2.75V with the 0.2C current discharge, obtained the capacity of battery normal temperature 0.2C current discharge to 2.75V; Repeat then above-mentioned charge step again with battery respectively with the current discharge of 1C, 3C and 5C, obtain battery normal temperature 1C, 3C and 5C current discharge capacity to 2.75V, calculate the discharge capacity ratio of battery under the different electric currents.Under the different electric currents in the discharge capacity ratio of battery and the discharge threshold voltage list in the table 2.
Table 2
From table 2 data as can be seen, adopt negative pole provided by the present invention, the big multiplying power discharging property of battery is significantly improved.
B, large current charge test
Under the room temperature condition, with battery respectively with the 0.2C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.2V, shelves 5 minutes; Battery, was shelved 5 minutes to 2.75V with the 1C current discharge, obtained the capacity of battery normal temperature 0.2C current charges to 4.2V; Then according to above-mentioned charge step respectively with 1C, 3C and 5C current charges, repeat above-mentioned discharge step, obtain battery normal temperature 1C, 3C and 5C current charges to 4.2V, 1C is discharged to the capacity of 2.75V, the discharge capacity ratio of battery when calculating under the different electric currents charging.Under the different charging currents in the discharge capacity ratio of battery and the charging threshold voltage list in the table 3.
Table 3
From table 3 data as can be seen, adopt negative pole provided by the present invention, the big multiplying power charging performance of battery is significantly improved.
2, security performance test
A, furnace temperature test
Under the room temperature condition, with battery respectively with the 1C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.2V, shelves 5 minutes; Carry out the test of 150 ℃ of stove heat, the observation battery had no abnormal after 1.5 hours, and measured the maximum temperature of battery surface.The observation situation of battery and the maximum temperature of battery surface are listed in the table 4.
Table 4
| Stove heat test 1.5 hours | The battery surface maximum temperature (℃) | |
| Embodiment 1 | Swell | ??151.3 |
| Comparative Examples 1 | Smolder | ??156.2 |
| Embodiment 2 | Swell | ??152.6 |
| Comparative Examples 2 | The explosion-proof valve cracking | ??157.1 |
| Embodiment 3 | Swell | ??154.7 |
| Comparative Examples 3 | The explosion-proof valve cracking | ??158.2 |
| Embodiment 4 | Leakage | ??152.0 |
| Comparative Examples 4 | Smolder | ??155.9 |
| Stove heat test 1.5 hours | The battery surface maximum temperature (℃) | |
| Embodiment 5 | Swell | ??152.9 |
| Comparative Examples 5 | Smolder | ??155.3 |
| Embodiment 6 | Swell | ??151.2 |
B, the test of negative terminal surface lithium concentration
Under the room temperature, with battery respectively with the 10C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.2V, shelves 5 minutes; Under the inert gas shielding atmosphere, battery is untied then, taken out negative pole, keep carrying out in low temperature, the atmosphere of inert gases XPS test (X-rayPhotoelectron Spectroscopy).The observation situation of each negative pole and the lithium concentration of negative terminal surface are listed in the table 5.
Table 5
| Negative terminal surface lithium concentration (percentage by weight) | |
| Embodiment 1 | ??17.8％ |
| Comparative Examples 1 | ??38.6％ |
| Embodiment 2 | ??19.7％ |
| Comparative Examples 2 | ??40.2％ |
| Embodiment 3 | ??15.6％ |
| Comparative Examples 3 | ??45.9％ |
| Embodiment 4 | ??23.7％ |
| Comparative Examples 4 | ??44.5％ |
| Embodiment 5 | ??19.6％ |
| Comparative Examples 5 | ??37.4％ |
| Embodiment 6 | ??19.0％ |
C, short-circuit test
Under the room temperature, with battery respectively with the 5C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.2V, shelves 5 minutes; Stick the thermometer thermocouple probe at battery surface then, battery is placed on both positive and negative polarity short circuit in the short-circuiting device.The observation situation of each battery and the maximum temperature of battery surface are listed in the table 6.
Table 6
| Battery The apparent phenomenon after the short circuit | The battery surface maximum temperature (℃) | |
| Embodiment 1 | Profile does not change | ??38.5 |
| Comparative Examples 1 | The explosion-proof valve cracking | ??145.1 |
| Embodiment 2 | Swell, not leakage | ??109.6 |
| Comparative Examples 2 | The explosion-proof valve cracking | ??152.3 |
| Embodiment 3 | Swell, cushion rubber leakage | ??116.8 |
| Comparative Examples 3 | The explosion-proof valve cracking | ??151.2 |
| Embodiment 4 | Swell, leakage | ??115.5 |
| Comparative Examples 4 | The explosion-proof valve cracking | ??155.9 |
| Embodiment 5 | Swell, leakage | ??110.7 |
| Comparative Examples 5 | The explosion-proof valve cracking | ??156.3 |
| Embodiment 6 | Swell, leakage | ??105.3 |
Negative pole provided by the present invention, reversible capacity and efficiency for charge-discharge obviously improve, and irreversible capacity obviously reduces, and has the problem that lithium lags behind of taking off hardly.The lithium rechargeable battery that adopts negative pole of the present invention to make has the energy density height, grows and favorable charge-discharge performance and security performance service time, and especially when high current charge-discharge, the battery that the present invention makes has more excellent performance.
Claims (10)
1. negative pole, this negative pole comprises collector and the negative material coating that loads on this collector, described negative material coating contains negative electrode active material and adhesive, described negative electrode active material is low crystalline carbon and metal lithium nitride, it is characterized in that, surface and/or described negative material coating that described metal lithium nitride is coated on described low crystalline carbon comprise two-layer at least, wherein said low crystalline carbon is arranged in the internal layer near collector, described metal lithium nitride is arranged in skin, and described internal layer is between skin and collector.
2. negative pole according to claim 1, wherein, described internal layer contains low crystalline carbon and adhesive, and the weight ratio of described low crystalline carbon and adhesive is 100: 0.3-100: 15; Described skin contains metal lithium nitride and adhesive, and the weight ratio of described metal lithium nitride and adhesive is 100: 0.3-100: 15.
3. according to any described negative pole in claim 1 or 2, wherein, the weight ratio of described low crystalline carbon and metal lithium nitride is greater than 1.
4. negative pole according to claim 3, wherein, the weight ratio of described low crystalline carbon and metal lithium nitride is 100: 30-100: 3.
5. according to claim 1,2 or 4 described negative poles, wherein, the d002 value of described low crystalline carbon is the 0.34-0.40 nanometer, and the Lc value is less than 60 nanometers, and the La value is less than 50 nanometers.
6. negative pole according to claim 5, wherein, described low crystalline carbon is resin carbon, organic polymer RESEARCH OF PYROCARBON, carbon black, petroleum coke, carbonaceous mesophase spherules, mesocarbon fiber and mixes at least a in the phosphorus pitch coke.
7. according to claim 1,2 or 4 described negative poles, wherein, described metal lithium nitride is Li
3-xM
xN, wherein M is at least a among Co, Mn, Ni, Cu, Al, Mg, Ga, Fe, Ti, V, Zn, Sn and the Cr, 0≤x≤0.7.
8. negative pole according to claim 7, wherein, described M is Cu and Ni or Co and Fe or Co and Mg.
9. negative pole according to claim 1, wherein, described collector is one or more in nickel, copper and the stainless steel, and described adhesive is one or more in sodium carboxymethylcellulose, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, ethylene/propylene/diene hydrocarbon terpolymer, sulfonated epdm, styrene/butadiene rubbers and the fluorubber.
10. lithium rechargeable battery, this battery comprises battery container, electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery container, described electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, it is characterized in that described negative pole is any described negative pole among the claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910001585A CN101783401A (en) | 2009-01-15 | 2009-01-15 | Cathode and Li-ion battery comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910001585A CN101783401A (en) | 2009-01-15 | 2009-01-15 | Cathode and Li-ion battery comprising same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101783401A true CN101783401A (en) | 2010-07-21 |
Family
ID=42523293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910001585A Pending CN101783401A (en) | 2009-01-15 | 2009-01-15 | Cathode and Li-ion battery comprising same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101783401A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709592A (en) * | 2012-06-01 | 2012-10-03 | 中国东方电气集团有限公司 | Lithium ion secondary battery and preparation method thereof |
| CN102751479A (en) * | 2011-04-19 | 2012-10-24 | 三星Sdi株式会社 | Anode active material, anode and lithium battery including the material, and method of preparing the material |
| CN105932334A (en) * | 2016-04-28 | 2016-09-07 | 深圳市力为锂能科技有限公司 | High-energy lithium ion battery and fabrication method thereof |
| CN106684367A (en) * | 2017-02-13 | 2017-05-17 | 济南大学 | Low-temperature petroleum coke negative electrode material coated with nitrogenous polymer pyrolytic carbon on surface and preparation method of low-temperature petroleum coke negative electrode material |
| CN107819105A (en) * | 2017-10-17 | 2018-03-20 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of silicon-carbon cathode pole piece |
| CN110048082A (en) * | 2019-04-03 | 2019-07-23 | 合肥国轩高科动力能源有限公司 | Reduce the method and gained pole piece of graphite negative electrode of lithium ion battery pole piece orientation value |
| CN111201640A (en) * | 2017-10-10 | 2020-05-26 | 日产自动车株式会社 | Electrode for nonaqueous electrolyte secondary battery |
-
2009
- 2009-01-15 CN CN200910001585A patent/CN101783401A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102751479A (en) * | 2011-04-19 | 2012-10-24 | 三星Sdi株式会社 | Anode active material, anode and lithium battery including the material, and method of preparing the material |
| CN102751479B (en) * | 2011-04-19 | 2016-02-03 | 三星Sdi株式会社 | Negative active core-shell material, containing its negative pole and the method for making of lithium battery and this material |
| US9350015B2 (en) | 2011-04-19 | 2016-05-24 | Samsung Sdi Co., Ltd. | Anode active material, anode and lithium battery including the material, and method of preparing the material |
| CN102709592A (en) * | 2012-06-01 | 2012-10-03 | 中国东方电气集团有限公司 | Lithium ion secondary battery and preparation method thereof |
| CN102709592B (en) * | 2012-06-01 | 2014-08-27 | 中国东方电气集团有限公司 | Lithium ion secondary battery and preparation method thereof |
| CN105932334A (en) * | 2016-04-28 | 2016-09-07 | 深圳市力为锂能科技有限公司 | High-energy lithium ion battery and fabrication method thereof |
| CN106684367A (en) * | 2017-02-13 | 2017-05-17 | 济南大学 | Low-temperature petroleum coke negative electrode material coated with nitrogenous polymer pyrolytic carbon on surface and preparation method of low-temperature petroleum coke negative electrode material |
| CN106684367B (en) * | 2017-02-13 | 2020-12-15 | 济南大学 | Low-temperature petroleum coke negative electrode material coated with nitrogen-containing polymer pyrolytic carbon and preparation method thereof |
| CN111201640A (en) * | 2017-10-10 | 2020-05-26 | 日产自动车株式会社 | Electrode for nonaqueous electrolyte secondary battery |
| CN107819105A (en) * | 2017-10-17 | 2018-03-20 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of silicon-carbon cathode pole piece |
| CN110048082A (en) * | 2019-04-03 | 2019-07-23 | 合肥国轩高科动力能源有限公司 | Reduce the method and gained pole piece of graphite negative electrode of lithium ion battery pole piece orientation value |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102088491B1 (en) | Negative electrode active material for lithium secondary battery and negative electrode for lithium secondary battery comprising the same | |
| CN101515640B (en) | Cathode and lithium ion secondary battery containing same | |
| US9123955B2 (en) | Negative active material, lithium battery including the material, and method for manufacturing the material | |
| US9034521B2 (en) | Anode material of excellent conductivity and high power secondary battery employed with the same | |
| EP2472654B1 (en) | Cathode active material, cathode, and nonaqueous electrolyte secondary battery | |
| CN108172823B (en) | Lithium-manganese-rich material, lithium ion battery positive electrode plate, lithium ion battery and preparation method thereof | |
| CN113471442B (en) | Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same | |
| WO2020135767A1 (en) | Positive electrode active material, positive electrode plate, electrochemical energy storage apparatus, and apparatus | |
| CN111370695B (en) | Negative electrode active material, and electrochemical device and electronic device using same | |
| CN109845005A (en) | Positive electrode active materials pre-dispersion composition, anode of secondary cell and the lithium secondary battery comprising the anode | |
| JP2012033481A (en) | Composite material for electrode, method for manufacturing the same, and lithium ion battery prepared therewith | |
| CN113611841B (en) | Secondary battery and method for manufacturing the same | |
| WO2010035681A1 (en) | Nonaqueous electrolyte secondary battery | |
| US20140227562A1 (en) | Lithium secondary-battery pack, electronic device using same, charging system, and charging method | |
| EP3503267A1 (en) | Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode | |
| KR20140013885A (en) | Lithium ion secondary battery | |
| WO2023065909A1 (en) | Electrochemical device and electronic device | |
| CN101783401A (en) | Cathode and Li-ion battery comprising same | |
| KR20150083382A (en) | Negative electrode and rechargeable lithium battery including same | |
| US20230387384A1 (en) | Method for Manufacturing Positive Electrode for Lithium Secondary Battery and Positive Electrode for Lithium Secondary Battery Manufactured Thereby | |
| JPH10261406A (en) | Carbon electrode and nonaqueous electrolyte secondary battery using it for negative electrode | |
| KR102439849B1 (en) | Negative active material for rechargeable lithium battery, and rechargeable lithium battery including the same | |
| KR20220148303A (en) | Anode composite and its application | |
| KR20220064385A (en) | Composite graphite material and manufacturing method thereof, secondary battery and device | |
| JP2023522656A (en) | Negative electrode mixture and its use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20100721 |