CN1870324A - Negative electrode of lithium ion secondary battery and lithium ion secondary battery containing the negative electrode - Google Patents
Negative electrode of lithium ion secondary battery and lithium ion secondary battery containing the negative electrode Download PDFInfo
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- CN1870324A CN1870324A CNA2005100349901A CN200510034990A CN1870324A CN 1870324 A CN1870324 A CN 1870324A CN A2005100349901 A CNA2005100349901 A CN A2005100349901A CN 200510034990 A CN200510034990 A CN 200510034990A CN 1870324 A CN1870324 A CN 1870324A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A negative electrode of lithium ion secondary cell consists of electrode base body and negative electrode activated material coating layer on said base body. It is featured as forming said negative electrode activated material by ball shaped natural graphite and carbon fiber as carbon fiber content being 0.5-10wt.% of negative electrode activated material total weight and obtaining volume density of 1.6g/cu.cm by using negative electrode activated material weight to divide negative electrode activated material costing layer volume.
Description
Technical field
The present invention relates to a kind of negative pole that is used for lithium rechargeable battery, and the lithium rechargeable battery that comprises this negative pole.
Background technology
Along with the remarkable development in recent years of portable electric appts, communication equipment and similar devices,, there is this tight demand to the secondary cell of high-energy-density from the viewpoint that economy, size, weight reduce.And lithium rechargeable battery is compared NI-G, Ni-MH battery has characteristics in light weight, that energy density is high, self discharge is little, circulation is good and is widely adopted.
The negative pole of lithium rechargeable battery mainly uses various material with carbon elements, the various alloy materials of studying in addition etc.This class material can both be inlayed and the removal lithium embedded ion.Wherein the material with carbon element of commercial extensive use at present is the graphite of crystalline state, and the main cause of using graphite is because he meets following requirement: (1) lithium storage capacity height; (2) existence of graphite in lithium ion is stable; (3) material with carbon element does not dissolve in electrolyte; (4) negative electrode density is than advantages such as height.Therefore also studying at present the negative pole that uses graphite, making it have higher capacity.
But, because the theoretical capacity of graphite is 372mah/g, so, very limited only from material itself to the high capacity of battery, unless can find a kind of alternative fully graphite, and the higher negative material of Capacity Ratio graphite.Therefore we consider from the bulk density that improves negative pole, and the method that increases the negative material of battery the inside by the raising bulk density improves energy density, thereby reach the purpose of raising capacity.The Japan Patent spy opens the once open mixture that proposes to adopt graphitized carbon fibre and graphite of 2000-195518 and Te Kai 2000-294283, and to access bulk density be 1.6g/cm
3Negative pole.But this negative material reaches 1.6g/cm in density
3The time, the problem of big multiplying power discharging property difference appears, and the reason difficulty that may to be negative pole be caused the absorption of electrolyte in negative pole to become by excessive calendering becomes lithium ion and is difficult to move in negative pole.
Open patent 2000-294283 discloses a kind of globular graphite and carbon fiber mixes the negative pole that forms.But this patent requires the circularity of globular graphite more than 0.86, otherwise may cause two kinds of negative material undercompoundings and cause irreversible capacity to increase, and high rate capability descends, the problem of aspects such as capacity reduction.More than cause capacity to reduce, the reason of high rate capability difference mainly is that negative pole is failed to form good electrical conductivity network after rolling in negative pole.
Summary of the invention
The technical problem to be solved in the present invention aims to provide a kind of negative pole of lithium rechargeable battery, not only has higher discharge capacity but also multiplying power discharging property is preferably arranged.
Another technical problem that the present invention will solve aims to provide a kind of lithium rechargeable battery with good discharge capacity and multiplying power discharging property.
For solving first technical problem, the invention provides a kind of negative pole of lithium rechargeable battery, comprise negative pole matrix and the negative electrode active material overlay that is coated on this matrix, described negative electrode active material comprises spherical native graphite and carbon fiber, wherein, the content of described carbon fiber accounts for 0.5～10 weight % of negative electrode active material total amount, the weight of described negative electrode active material divided by negative electrode active material overlay volume calculate bulk density be 1.6g/cm
3Or more than.
Wherein, the content of described carbon fiber is preferably 1.0～5.0 weight % that account for the negative electrode active material total amount.
Wherein, the average grain diameter of described spherical native graphite is 5-20 μ m.
Wherein, the BET specific area of described spherical native graphite is 4-10m
2/ g.
Wherein, the diameter of described carbon fiber is 100～500nm, and draw ratio is 10～5000.
Wherein, described carbon fiber has 1 * 10
-4～5 * 10
-4The resistivity of Ω * CM.
For solving second technical problem, the invention provides a kind of lithium rechargeable battery, comprise positive pole, negative pole, electrolyte and place barrier film between the both positive and negative polarity, be closed in the battery case in the lump, wherein, described negative pole comprises negative pole matrix and the negative electrode active material overlay that is coated on this matrix, described negative electrode active material is made of spherical native graphite and carbon fiber, wherein, the content of described carbon fiber accounts for 0.5～10 weight % of negative electrode active material total amount, the weight of described negative electrode active material divided by negative electrode active material overlay volume calculate bulk density be 1.6g/cm
3More than.
Wherein, described positive pole comprises anodal matrix and the positive active material overlay that is coated on this matrix, and described positive active material is selected chemical formula Li for use
xNi
1-yCo
yO
2, Li
xMn
2-yB
yO
2The expression material in one of or its mixture, B is a transition metal or nonmetal in the formula, 0.9≤x≤1.1,0≤y≤1.
Compared with prior art, the invention has the advantages that, because need there be electron propagation ducts in electronics in the conduction of negative pole, and graphite granule has only by the collision between the particle and finishes, along with the embedding of lithium ion in the charge and discharge process with take off embedding, the continuous expansion of active material particle descends the active material contact point, cause collision probability to descend, the multiplying power discharging property of battery descends, carbon fiber provided by the invention can form a huge electric transmission network between active material, improved the conductance of electrode greatly.Carbon fiber provided by the invention in addition has big draw ratio, when forming the electric transmission network easily, has imbibition ability more carefully, cause electrolyte to absorb the problem of difficulty thereby can solve, significantly improve battery cycle life because negative pole graphite excessively rolls.And the specific insulation of carbon fiber of the present invention is lower, and battery is had improvement than the discharge performance of high magnification.
Embodiment
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
The negative pole of a kind of lithium rechargeable battery of the present invention, comprise negative pole matrix and the negative electrode active material overlay that is coated on this matrix, described negative pole matrix be known in those skilled in the art can be in electrochemical reaction the conductivity carrier of stable existence, for example can be Copper Foil.Described negative electrode active material comprises spherical native graphite and carbon fiber.
In the negative pole of the present invention, described spherical native graphite there is no particular determination so long as the native graphite of the shape spheroidization of graphite particle is got final product.There is no particular limitation to the shape of particle of spherical native graphite, not only can be the spherical shape of shape such as football or cabbage shape, also can be the ellipsoid as the olive shape.Can adopt the commercially available prod, or make with the method for following industry, to be that the particle of raw material is dissolved in the tarvia for example with the flakey native graphite, oven dry, make particle independent with physical method,, cool off more than 3 hours in roasting under the high temperature more than 1000 ℃ then, can obtain needed spherical native graphite.
Among the present invention, the BET specific area of spherical native graphite is 4m more fortunately
2More than/the g, 10m
2Below/the g, the not enough 4m of BET specific area
2During/g, easy and electrolyte generation side reaction, the BET specific area surpasses 10m
2During/g, when forming the SEI film, graphite surface can consume too much electrolyte.The average grain diameter of spherical native graphite is preferably 5-20 μ m, the interplanar distance d of (002) face in the X diffraction pattern
002Preferably between 0.3354-0.3357.
In the negative pole of the present invention, there is no particular limitation to carbon fiber, can obtain from commercially available method, and also can be to be prepared from by conventional method.Such as being the whisker that generates by gas phase, also can be that methods such as matrix method, spray process are prepared from.Optimum fiber diameter 100-500nm, the carbon fiber of draw ratio 10-5000 can guarantee the absorbent of carbon fiber like this, and is the most favourable to the cycle performance of battery.Preferred resistivity is 1 * 10
-4～5 * 10
-4The carbon fiber of Ω * CM because the specific insulation of this carbon fiber is lower, therefore guarantees the reduction of negative electrode specific insulation, improves the big multiplying power discharging property of battery.Among the present invention, the content of the carbon fiber in the negative electrode active material is the 0.5-10 weight % that accounts for the negative electrode active material total amount, preferred 1.0-5.0 weight %.Because if carbon fiber content less than 0.5 weight %, can not provide a cycle characteristics preferably on the one hand, can not guarantee on the other hand to form good electron conduction network at negative pole, influence multiplying power discharging.Content when promptly pole plate being rolled, makes the bulk density of negative electrode active material overlay not reach 1.6g/cm greater than the bulk density that 10 weight % then can significantly influence negative pole
3Even perhaps reach 1.6g/cm
3, but destroyed the negative pole graphite particle, thereby influenced the discharge capacity and the energy density of battery.
In the negative pole of the present invention, negative active core-shell material as long as in the scope of not damaging effect of the present invention, can also contain conventional negative material in the past except containing above-mentioned spherical natural graphite and carbon fiber.In the negative active core-shell material of the present invention, preferably contain spherical natural graphite 90-99.5 weight %.
Negative pole of the present invention makes with following method:
At first spherical native graphite and binding material, the water with ormal weight is mixed into spherical native graphite slurry; Carbon fiber and binding material, the water of ormal weight are mixed into the carbon fiber slurry; Two kinds of slurries are mixed, be modulated into cathode size.Cathode size is coated on the two sides of Copper Foil collector body, and dry back roll-in also is cut into the size of respective specified size.For realizing purpose of the present invention, the bulk density of negative pole is at 1.6g/cm after the roll-in
3Or more than, promptly the weight of negative electrode active material divided by negative electrode active material overlay volume calculate bulk density be 1.6g/cm
3Or more than, because the negative pole bulk density is if be lower than 1.6g/cm
3, can make the capacitance of battery and energy density reduce the requirement that does not reach good discharge capacity and energy density.
Tackifier in the above-mentioned binding material are selected from: methylcellulose (MC), CMC (CMC), carboxymethyl hydroxyethyl cellulose (CMHEC), hydroxypropyl methylcellulose (HPMC) and hydroxypropyl cellulose (HPC) one of them or its mixture, and consumption is the 0.5-10wt% of negative electrode active material; Binding agent is one of them or its mixture of butadiene-styrene rubber (SBR) and polytetrafluoroethylene (PTFE), and consumption is the 1-10wt% of negative electrode active material.
A kind of lithium rechargeable battery provided by the present invention comprises positive pole, negative pole, electrolyte and places barrier film between the both positive and negative polarity that be closed in the lump in the battery case, wherein said negative pole adopts the negative pole of the invention described above.
Among the present invention, consisting of of described positive pole is conventionally known to one of skill in the art, comprises anodal matrix and the positive active material overlay that is coated on this matrix.Described anodal matrix is conventionally known to one of skill in the art, for example can be selected from aluminium foil.Described positive active material is not particularly limited, and for conventionally known to one of skill in the art, preferably uses chemical formula Li
xNi
1-yCo
yO
2, Li
xMn
2-yB
yO
2The expression material in one of or its mixture, B is a transition metal or nonmetal in the formula, 0.9≤x≤1.1,0≤y≤1.Also contain adhesive in the described positive active material overlay, the kind of described adhesive and content are conventionally known to one of skill in the art, for example fluorine resin and polyolefin compound are as in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR) one or more.In general, the content of described adhesive is the 0.01-8 weight % of positive active material, is preferably 1-5 weight %.Described positive electrode active materials can also comprise anodal conductive agent, to improve anodal conductivity.The kind of described anodal conductive agent and content are conventionally known to one of skill in the art, for example, can be selected from acetylene black, conductive carbon black, electrically conductive graphite, carbon fiber or metallic conduction additive, its content is the 0-15 weight % of positive active material, is preferably 1-10 weight %.
Nonaqueous electrolytic solution of the present invention is made up of nonaqueous solvents and the electrolyte that is dissolved in nonaqueous solvents.Above-mentioned nonaqueous solvents is not particularly limited, and can be the nonaqueous electrolytic solution of this area routine, for example is to use the mixed solvent of chain acid esters and ring-type acid esters.The chain acid esters be selected from dimethyl carbonate, diethyl carbonate, ethyl propyl carbonic acid ester, diphenyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, dimethoxy-ethane, diethoxyethane with and fluorine-containing, sulfur-bearing and contain one of them or its mixture of the chain organosilane ester of unsaturated bond; The ring-type acid esters be selected from ethylene carbonate, propene carbonate, vinylene carbonate, gamma-butyrolacton, sultone with and fluorine-containing, sulfur-bearing or contain one of them or its mixture of the ring-type organosilane ester of unsaturated bond.The electrolyte that dissolves in above-mentioned nonaqueous solvents, there is no particular limitation equally in the present invention, can use the electrolyte that is generally used for nonaqueous electrolytic solution secondary battery.As: one of be selected from the lithium salts of lithium perchlorate, chlorine lithium aluminate, lithium hexafluoro phosphate, LiBF4, lithium halide, fluorocarbon based fluorine oxygen lithium phosphate or fluorocarbon based sulfonic acid lithium or its mixture.Preferably by by electrolytic salt lithium hexafluoro phosphate LiPF
6With the concentration of compositions such as non-aqueous solvent dimethyl carbonate EC, ethylene carbonate DEC, carbonic acid diene ester DMC be the nonaqueous electrolyte of 1M.
Among the present invention, described barrier film is not particularly limited, and can be barrier film conventional in the lithium rechargeable battery, preferred polyolefm micro-porous film.
Except that above-mentioned, other materials and parts used among the present invention all are not particularly limited, and can adopt the material and the parts of present technique field routine.Obtain making square aluminum case lithium ion secondary cell according to known method behind positive pole, negative pole, nonaqueous electrolytic solution, the barrier film according to above-mentioned described method.
Below in conjunction with embodiment, reach performance evaluation to corresponding lithium ion battery, the present invention will be further explained and explanation, to verify purpose of the present invention.Prepared rectangular lithium ion battery is the 453450A type among the embodiment, promptly highly be 50mm, thickness is 4.5mm, width is the rectangular lithium ion battery of 34mm, but the present invention is not limited to rectangular lithium ion battery, various lithium ion secondary battery with nonaqueous electrolyte such as that the present invention is fit to equally is cylindrical, coin shape.Described embodiment only is used to the present invention is described but is not limited to the present invention.
Embodiment 1
With a certain amount of PVDF (Atuofeina Corp's commodity, 761#PVDF) be dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP) with certain ratio, with LiCoO2 (FMC commodity) and acetylene black (U.S.'s Cabot commodity, XC-72) join in this solution, the fully mixed anode sizing agent that gets, it consists of LiCoO2: acetylene black: PVDF=94: 3: 3.This slurry is uniformly applied on the aluminium foil of 20 μ m, through 125 ℃ of dryings.Obtain the thick positive plate of about 125 μ m after the calendering.
A certain amount of CMC (CMC) and butadiene-styrene rubber (SBR) are dissolved in the water with certain proportion, make binder solution.Spherical native graphite is joined in the binder solution, mixed spherical native graphite slurry, it consists of spherical native graphite: CMC: SBR=93: 2: 5.Carbon fiber (clear and electrician's commodity, model VGCF, fibre diameter 150nm, draw ratio 100) is joined in the binder solution, the mixed carbon fiber slurry that gets, it consists of carbon fiber: CMC: SBR=60: 15: 25.The carbon fiber slurry is joined in the spherical native graphite slurry, the fully mixed cathode size that gets, it finally consists of spherical native graphite: carbon fiber: CMC: SBR=99.5: 0.5: 2: 5.To mix on the Copper Foil that the back cathode size is coated on 12 μ m equably and through 125 ℃ of dryings.Obtaining bulk density after the calendering is 1.6g/cm
3Above negative plate.
The PP membrane coil coiled rectangular lithium ion battery electricity core that above-mentioned positive and negative plate and 20 μ m are thick is in the battery case of packing into and weld, subsequently with LiPF
6Concentration with 1mol/l is dissolved in EC/DMC=1: formed electrolyte is injected in the battery case in 1 the mixed solvent, and the lithium rechargeable battery of 453450A is made in sealing.
Embodiment 2
Except carbon fiber (clear and electrician's commodity, model VGCF-H, the amount of adding fibre diameter 150nm, draw ratio 60) changes the spherical native graphite that consists of of back cathode size: carbon fiber: CMC: SBR=99: outside 1: 2: 5, other making step is all identical with embodiment 1 with condition.
Embodiment 3
Except the amount of the adding of carbon fiber VGCF-H changes the spherical native graphite that consists of of back cathode size: carbon fiber: CMC: SBR=98: 2: 2: 5, other making step and condition all with
Embodiment 1 is identical.
Embodiment 4
Except the amount of the adding of carbon fiber VGCF-H changes the spherical native graphite that consists of of back cathode size: carbon fiber: CMC: SBR=95: 5: 2: 5, other making step and condition all with
Embodiment 1 is identical.
Embodiment 5
Except the amount of the adding of carbon fiber VGCF-H changes the spherical native graphite that consists of of back cathode size: carbon fiber: CMC: SBR=90: 10: 2: 5, other making step is all identical with embodiment 1 with condition.
Comparative Examples 1
Except the amount of the adding of carbon fiber VGCF-H changes the spherical native graphite that consists of of back cathode size: carbon fiber: CMC: SBR=85: 15: 2: 5, other making step is all identical with embodiment 1 with condition.
Comparative Examples 2
Consist of the flakey Delanium except what the addition of carbon fiber VGCF-H and negative pole graphite changed the back cathode size: carbon fiber: CMC: SBR=98: 2: 2: 5, other making step is all identical with embodiment 1 with condition.
Comparative Examples 3
Except not adding carbon fiber in the negative pole, the component of cathode size is spherical native graphite: CMC: SBR=100: outside 2: 5, other making step is all identical with embodiment 1 with condition.
[test]
Table 1
| Test portion | The graphite ratio | The carbon fiber ratio | Bulk density (g/cm 3) | |
| Spherical native graphite | The scale Delanium | |||
| Embodiment 1 | 99.5 | / | 0.5 | 1.63 |
| Embodiment 2 | 99 | / | 1 | 1.62 |
| Embodiment 3 | 98 | / | 2 | 1.62 |
| Embodiment 4 | 95 | / | 5 | 1.62 |
| Embodiment 5 | 90 | / | 10 | 1.61 |
| Embodiment 6 | 90 | / | 10 | 1.60 |
| Comparative Examples 1 | 85 | / | 15 | 1.55 |
| Comparative Examples 2 | / | 98 | 2 | 1.43 |
| Comparative Examples 3 | 100 | / | 0 | 1.63 |
As can be seen from Table 1, the negative material bulk density of embodiment can both reach 1.6g/cm
3, and the carbon fiber in the Comparative Examples 1 surpasses 10wt%, bulk density has only 1.55g/cm
3, will certainly influence the capacity and the energy density of battery.
[cell evaluation]
1, battery capacity
With the above-mentioned rectangular lithium ion battery that makes with the constant current charge of 400mA to 4.2V, constant-potential charge then, cut-off current 20mA; Constant current with 800mA discharges cut-ff voltage 3.0V again.Record the capacity and the internal resistance of battery.
2, cycle characteristics
The above-mentioned square lithium ion secondary battery that makes is discharged and recharged 300 circulations with above-mentioned charge and discharge system degree.Measure the capacity sustainment rate after 300 circulations.
3, multiplying power discharging
After the above-mentioned square lithium ion secondary battery that makes charged to 4.2V with said method, constant current discharge with 160mA, cut-ff voltage 3.0V, record the 0.2C capacity of battery, being full of the electricity back more in the same manner is the constant current discharge of 1600mA with the 2C multiplying power, cut-ff voltage 3.0V records the 2C capacity of battery.The 2C/0.2C discharging efficiency of counting cell.
4, above result of experiment is as follows:
| Battery | Initial discharge capacity (mAh) | Internal resistance (m Ω) | 2C/0.2C multiplying power discharging (%) | Surplus ratio (%) after 300 circulations |
| Embodiment 1 | 833 | 47 | 85 | 83.2 |
| Embodiment 2 | 835 | 45 | 89.9 | 86.7 |
| Embodiment 3 | 829 | 43 | 90.3 | 88.7 |
| Embodiment 4 | 828 | 41 | 91.2 | 89.0 |
| Embodiment 5 | 820 | 41 | 91.9 | 87.7 |
| Embodiment 6 | 819 | 40 | 93.7 | 87.1 |
| Comparative Examples 1 | 782 | 37 | 95.2 | 88.8 |
| Comparative Examples 2 | 776 | 42 | 91 | 89.0 |
| Comparative Examples 3 | 815 | 55 | 75.3 | 65 |
5, conclusion:
Use negative active core-shell material provided by the invention to have higher capacity, cycle life and multiplying power discharging characteristic preferably preferably as the lithium rechargeable battery of negative pole comprising the carbon fiber of the spherical native graphite of 90-99.5wt% and 0.5-10wt%.
Claims (8)
1. the negative pole of a lithium rechargeable battery, comprise negative pole matrix and the negative electrode active material overlay that is coated on this matrix, described negative electrode active material comprises spherical native graphite and carbon fiber, wherein, the content of described carbon fiber accounts for 0.5～10 weight % of negative electrode active material total amount, the weight of described negative electrode active material divided by negative electrode active material overlay volume calculate bulk density be 1.6g/cm
3Or more than.
2. the negative pole of a kind of lithium rechargeable battery according to claim 1, wherein, the content of described carbon fiber accounts for 1.0～5.0 weight % of negative electrode active material total amount.
3. the negative pole of a kind of lithium rechargeable battery according to claim 1, wherein, the diameter of described carbon fiber is 100～500nm, draw ratio is 10～5000.
4. the negative pole of a kind of lithium rechargeable battery according to claim 1, wherein, described carbon fiber has 1 * 10
-4～5 * 10
-4The resistivity of Ω * CM.
5. the negative pole of a kind of lithium rechargeable battery according to claim 1, wherein, the BET specific area of described spherical native graphite is 4-10m
2/ g.
6. the negative pole of a kind of lithium rechargeable battery according to claim 1, wherein, the average grain diameter of described spherical native graphite is 5-20 μ m.
7. lithium rechargeable battery comprises positive pole, negative pole, electrolyte and places barrier film between the both positive and negative polarity that be closed in the lump in the battery case, wherein, described negative pole is the negative pole as each described lithium rechargeable battery of claim 1-6.
8. a kind of lithium rechargeable battery according to claim 7, wherein, described positive pole comprises anodal matrix and the positive active material overlay that is coated on this matrix, described positive active material is selected chemical formula Li for use
xNi
1-yCo
yO
2, Li
xMn
2-yB
yO
2The expression material in one of or its mixture, B is a transition metal or nonmetal in the formula, 0.9≤x≤1.1,0≤y≤1.
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|---|---|---|---|
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|---|---|---|---|
| CNB2005100349901A CN100438145C (en) | 2005-05-29 | 2005-05-29 | Negative electrode of lithium ion secondary battery and lithium ion secondary battery containing the negative electrode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697227A (en) * | 2019-03-12 | 2020-09-22 | 丰田自动车株式会社 | Lithium ion secondary battery and method for manufacturing same |
| CN111710851A (en) * | 2020-04-27 | 2020-09-25 | 常州赛得能源科技有限公司 | Solid-state battery and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5244757A (en) * | 1991-01-14 | 1993-09-14 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
| JPH08315820A (en) * | 1995-05-11 | 1996-11-29 | Petoca:Kk | Carbon fiber for secondary battery negative electrode material and manufacture thereof |
| JP3663864B2 (en) * | 1997-12-16 | 2005-06-22 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
| JP2000195518A (en) * | 1998-12-28 | 2000-07-14 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| KR100567112B1 (en) * | 2002-07-08 | 2006-03-31 | 마쯔시다덴기산교 가부시키가이샤 | Negative electrode and lithium ion secondary battery using the same |
| JP4252847B2 (en) * | 2003-06-09 | 2009-04-08 | パナソニック株式会社 | Lithium ion secondary battery |
| CN2640052Y (en) * | 2003-08-19 | 2004-09-08 | 比亚迪股份有限公司 | Lithium ion secondary battery |
-
2005
- 2005-05-29 CN CNB2005100349901A patent/CN100438145C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697227A (en) * | 2019-03-12 | 2020-09-22 | 丰田自动车株式会社 | Lithium ion secondary battery and method for manufacturing same |
| CN111697227B (en) * | 2019-03-12 | 2023-03-14 | 丰田自动车株式会社 | Lithium ion secondary battery and method for manufacturing same |
| CN111710851A (en) * | 2020-04-27 | 2020-09-25 | 常州赛得能源科技有限公司 | Solid-state battery and preparation method thereof |
| CN111710851B (en) * | 2020-04-27 | 2022-04-01 | 常州赛得能源科技有限公司 | Solid-state battery and preparation method thereof |
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