CN101127394A - A lithium secondary battery cathode including graphite and its making method - Google Patents
A lithium secondary battery cathode including graphite and its making method Download PDFInfo
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- CN101127394A CN101127394A CNA2006100621286A CN200610062128A CN101127394A CN 101127394 A CN101127394 A CN 101127394A CN A2006100621286 A CNA2006100621286 A CN A2006100621286A CN 200610062128 A CN200610062128 A CN 200610062128A CN 101127394 A CN101127394 A CN 101127394A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000010439 graphite Substances 0.000 title claims abstract description 73
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 11
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- 239000006257 cathode slurry Substances 0.000 claims abstract description 4
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- 239000002002 slurry Substances 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 210000000481 breast Anatomy 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000013081 microcrystal Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 229910021383 artificial graphite Inorganic materials 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 239000006229 carbon black Substances 0.000 abstract 1
- 238000005538 encapsulation Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 239000003125 aqueous solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 241000209456 Plumbago Species 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000006253 pitch coke Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- XIRVPWMOJMFUOQ-UHFFFAOYSA-N [Li].C(C(=C)C)(=O)O Chemical compound [Li].C(C(=C)C)(=O)O XIRVPWMOJMFUOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- -1 methacrylic acid ethylene oxide ester Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The utility model discloses a graphite-based lithium secondary battery cathode. Take the weight into calculation, the components are: natural graphite : artificial graphite : conducting agent : bonding aids : bonding agent : solvent equals 10 to 90 : 10 to 90 : 1 to 10 : 1 to 10 : 1 to 10 : 100 to 200. The diameter range of the natural graphite grain is 10 to 30Mum, the diameter range of the artificial graphite grain is 10 to 30Mum, and the grain diameter range of the conducting agent is 1 to 30Mum. The natural graphite is in spherical shape, flake shape or crystallite shape, and the conducting agent is natural flake, crystallite graphite, conducting carbon black or acetylene black. The utility model also discloses the manufacturing method of the graphite-based lithium secondary cell cathode. The utility model overcomes the shortage of the prior art that the net natural graphite requires encapsulation and modification before introduced into the lithium ion cell cathode system. The purpose toward longer cycle life and lower production cost can be achieved by optimizing the application formula of natural and artificial graphite as well as the preparation method of cathode slurry.
Description
Technical field
The present invention relates to lithium secondary battery and make the field, be specifically related to contain the lithium secondary battery anode slurry and the manufacture method thereof of graphite.
Technical background
Lithium ion battery is a kind of brand-new Green Chemistry power supply, compares with traditional nickel-cadmium cell, Ni-MH battery to have the voltage height, and the life-span is long, the advantage that energy density is big.After nineteen ninety, Sony corporation of Japan was released first generation lithium ion battery, it had been developed and has been widely used in rapidly various portable sets.
Native graphite has capacity height, cheap, the abundant advantage of originating as lithium ion battery negative material, but also exist first charge-discharge efficiency low simultaneously, cycle performance is poor, the shortcoming high to the electrolyte selectivity, thus limited its extensive use in lithium ion battery.This mainly is the surface texture characteristics decision by native graphite: formed passivating film SEI (Sofidelectrolyte interfaee) film has inhomogeneities and fragility in the embedding lithium process first, can not adapt to graphite material volume and surperficial variation in the charge and discharge process well.Therefore, the graphite material that chemical property is good should form on its surface and contain the SEI film of elastic component, thereby prevents in the charge and discharge process owing to graphite volume and the surperficial destruction that changes the SEI film that causes.
J.Power sources 81-82 (1999) 368-378 has reported at graphite surface and has plated layer of metal film as Ag, Au, Bi, In, Pb, Pd, Sn, Zn etc. by vacuum.J.Electrochem.Soc., 147 (4) 1280-1285 (2000) have reported and have used the method for chemical plating at native graphite surface deposition layer of metal copper particle.These methods can obviously be improved graphite electrochemistry performance.Thereby its principle is these metals on the one hand and can forms alloy with lithium ion but do not hinder the migration raising capacity of lithium ion; The metal film that plates has on the other hand changed charcoal negative terminal surface SEI film and has formed mechanism.
A large amount of research has also been done for the modification of native graphite by domestic many manufacturers, Institute of Chemistry, Academia Sinica's patent (application number: 0113639.6) disclose a kind of method of modifying of native graphite: native graphite is joined in the inorganic acid that concentration is 1-50%, heat down and stirred 1-100 hour at 20-80 ℃, then filtering drying; Is 1 with the native graphite after the above-mentioned processing with polystyrolsulfon acid lithium, weight ratio: the methacrylic acid ethylene oxide ester of 0-1 and methacrylic acid lithium, weight ratio are 1: own sulfonic acid lithium of the acrylonitrile of 0-1 and methacrylic acid or the own sulfonic acid lithium of methacrylic acid are by weight 1: 0-0.50 fully mixes in decentralized medium, obtains the graphite material that surface adsorption has monomer or polymer; There is the graphite material of monomer or polymer to transfer in the radiant tube above-mentioned surface adsorption, under radiation source, carries out the reaction of radiation polymerization or crosslinking with radiation then, obtain polymer solid electrolyte coated graphite material, and then use solvent clean.
Said method all is some very promising methods, but method technology and complicated operation, but production cost is higher, is unfavorable for extensive use.
Summary of the invention
At the shortcoming that present native graphite needs modification to use, the object of the present invention is to provide a kind of negative pole and manufacture method thereof that native graphite and Delanium is directly applied to battery on battery.
For realizing above-mentioned technical purpose, the present invention by the following technical solutions:
A kind of lithium secondary battery anode that contains graphite contains native graphite and Delanium.
Further, by weight, native graphite: Delanium: additional adhesive: binding agent: solvent=10～90: 10～90: 1～10: 1～10: 100～200, native graphite+Delanium=100 wherein.Particle size range 10～30 μ m of described natural graphite particles, described Delanium particle grain size scope 10～30 μ m.The effect of binding agent mainly is will be with firm being bonded on the Copper Foil of pole piece, and itself does not have electro-chemical activity, and the amount of adding too much can influence the specific discharge capacity of negative plate equally.The effect of solvent is that slurry is mixed, and less words can't mixing, and more words are very rare, are unfavorable for the coating of slurry.
Further, also comprise and be no more than 10 parts conductive agent, the conductive agent particle size range is 1～30 μ m.An amount of adding of conductive agent can well strengthen the electric conductivity of negative plate, thereby reduces the hysteresis of charge and discharge process, improves cycle performance.But the capacity of conductive agent itself is lower, and addition too much can reduce the quality capacity performance of whole negative plate, and is therefore proper in 1～10 amount.
Preferably, native graphite: Delanium: additional adhesive: binding agent: solvent=50: 50: 2.5: 3.5: 2: 145.
Described native graphite is one or more in sphere, scale or the crystallite shape graphite, described Delanium is all kinds of through high temperature carbonization and graphitized carbon material, and described conductive agent is one or more in natural scale, micro crystal graphite, conductive carbon black or the acetylene black.
The manufacture method of above-mentioned lithium secondary battery anode comprises the preparation of cathode size, and the preparation of described cathode size comprises the steps:
The preparation of step 1, binding agent glue: place mixer to stir the 50%-90% of binding agent and total solvent;
Step 2, natural graphite particles and Delanium and conductive agent done in de-airing mixer mix, divide 2-3 to criticize then to add the binding agent glue of 10%～80% step 1 preparation and stir;
Step 3, adding additional adhesive butadiene-styrene rubber breast SBR also stir;
The binding agent glue of step 4, the remaining step 1 preparation of adding also stirs;
Step 5, branch 1-3 criticize the remaining solvent of adding and stir;
Step 6, the slurry after step 5 stirred are finished the sky through vacuumizing, sieving
The preparation of right graphite cathode slurry.
Bonding agent is generally CMC (sodium carboxymethylcellulose) or PVDF (polyvinylidene fluoride) in the above-mentioned steps, and solvent is generally water or NMP (N-methyl pyrrolidone), and when bonding agent was CMC, solvent was a water, and when bonding agent was PVDF, solvent was NMP.
The 50%-90% of total solvent divides 2-5 part in the above-mentioned steps one, adds in batches.
All to stir 10 minutes-12 hours after every part of solvent adds in the above-mentioned steps, preferred 30 minutes-3 hours, it be stirred.
In the above-mentioned steps, native graphite is one or more in sphere, scale or the crystallite shape graphite, Delanium is all kinds of process high temperature carbonizations and graphitized carbon materials such as pitch coke, and conductive agent is one or more in natural scale, micro crystal graphite, conductive carbon black or the acetylene black.
Doing the time of mixing in the above-mentioned steps two is 10 minutes-12 hours, and it is stirred.
When the binding agent that divides 2-3 to criticize the preparation of adding 10%～80% step 1 in the above-mentioned steps two stirs, after adding, all to stir 10 minutes-12 hours by every part of binding agent with the 1Hz-1000Hz revolution, preferred 20Hz-200Hz revolution was stirred 30 minutes-3 hours, and it is stirred.
In the above-mentioned steps three, behind the adding additional adhesive butadiene-styrene rubber breast SBR, stirred 10 minutes-12 hours with 1Hz-1000Hz revolution and rotation, preferred 20Hz-200Hz revolves round the sun and rotation was stirred 30 minutes-3 hours, and it is stirred.
In the above-mentioned steps five, when dividing 1-3 to criticize to add remaining solvent, after every part of solvent adds, stirred 10 minutes-12 hours with 1Hz-1000Hz revolution and rotation, preferred 20Hz-200Hz revolution and rotation stirring 30 minutes-3 hours stir it.
In the above-mentioned steps six, stirring slurry at last and vacuumizing is to stir 10 minutes-12 hours with the 1Hz-1000Hz revolution, and the limit revolution is stirred the limit and vacuumized, and it is stirred.
Adopt technique scheme, beneficial technical effects of the present invention is: because native graphite is applied directly to lithium-ion battery system and exists the very poor problem of cycle life, domestic and international many scholars, all be to adopt the native graphite coating modification and then be incorporated into the lithium ion battery negative system, these methods waste time and energy.The present invention uses by the collocation of native graphite and Delanium and the preparation method that improves cathode size reaches the purpose that improves native graphite cycle life, effect is very obvious, owing to directly native graphite and Delanium are applied to make negative pole, the production cost of battery has had reduction to a certain degree simultaneously.
Description of drawings
Fig. 1 is the capability retention figure of the embodiment of the invention 1 battery;
Fig. 2 is the capability retention figure of the embodiment of the invention 2 batteries;
Fig. 3 is the capability retention figure of the embodiment of the invention 3 batteries;
Fig. 4 is the capability retention figure of the embodiment of the invention 4 batteries;
Embodiment
Embodiment 1
A kind of lithium secondary battery anode that contains graphite and preparation method thereof, by weight, each composition ratio of lithium secondary battery anode is: natural spherical plumbago: pitch coke Delanium: natural flake graphite conductive agent: additional adhesive SBR: binding agent CMC: aqueous solvent=50: 50: 2.5: 3.5: 2: 145.
The cathode size preparation method:
1) preparation binding agent glue, at first with 28% of binding agent CMC (sodium carboxymethylcellulose) and adding aqueous solvent, (can be the mixer of eggbeater or other type) stirs in mixer, mixing time is 40 minutes, and then 20% continuation stirring of adding aqueous solvent, mixing time is 10 minutes, adds 32% of solvent at last and stirs, mixing time is 10 minutes, finishes preparation binding agent glue process.
2) preparation slurry: with the natural spherical plumbago particle, Delanium particle and natural flake graphite conductive agent stirred 1 hour with the 10Hz revolution in de-airing mixer, the binding agent glue of adding 15% stirred 1 hour with the 10Hz revolution, adding 40% binding agent glue again stirred 1 hour with the 20Hz revolution, adding butadiene-styrene rubber breast SBR again stirred 0.5 hour with 25Hz revolution and rotation, adding remaining 45% binding agent glue then stirred 10 minutes～12 hours with 38Hz revolution and rotation, add again aqueous solvent 10% with 38Hz revolution and rotation stirring 1 hour, at last remaining 10% aqueous solvent is all added with 38Hz revolution and rotation stirring and finished pulping process in 2 hours, slurry was sieved with 10Hz revolution and vacuum in 20 minutes finish the preparation of natural graphite cathode slurry again.
In above-mentioned preparation process, because the adhesive property of the binding agent glue of the amount of different solvents preparation is different, the purpose that in batches adds solvent is in order to make cathode size mix more evenly, to divide two steps to add solvent and help regulating the viscosity of slurry and active material graphite is uniformly dispersed.Dividing two steps adding binding agents to help binding agent mixes.The purpose that in batches adds graphite is to prevent the local graphite reunion.The control of mixing time is to stir under the situation of surface topography that can not dilapidated graphite.
The test of negative pole specific capacity, negative plate is made in the cathode size coating of preparation, electrolyte is 1mol/1LiF6PO4 EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) (1: 1: 1), metal lithium sheet is to electrode, be assembled into the specific capacity of the negative pole of button cell test preparation, the specific capacity that records negative pole is 342mAh/g.
Other arrange in pairs or groups positive plate of LiCoO2 preparation, electrolyte is three component mixed solvent EC: the DMC: EMC=1: 1: 1 of 1MLiF6PO4, adopt commercial micro-pore septum to be assembled into the finished product battery, speed with 1C discharges and recharges experiment, discharging and recharging deboost is 4.2V～3V, the circulation conservation rate C that test battery is 300 times
300/ C
1It is discharge capacity 342mAh/g that table 1 has provided the negative pole specific capacity that records, and 300 times the circulation volume conservation rate is 91.23%.Capacity keeps curve as shown in Figure 1.
Embodiment 2
Another kind contains lithium secondary battery anode of graphite and preparation method thereof, by weight, each composition ratio of lithium secondary battery anode is: natural spherical plumbago: MCMB (MCMB): additional adhesive SBR: binding agent CMC: aqueous solvent=50: 50: 3.5: 2: 145.The preparation method of cathode size is with embodiment 1, and button cell specific capacity and the test of finished product cycle performance of battery are with embodiment 1.
It is discharge capacity 346mAh/g that table 1 has provided the specific capacity that records negative pole, and 300 times the circulation volume conservation rate is 90.51%, and capacity keeps curve as shown in Figure 2.
Embodiment 3
Another contains lithium secondary battery anode of graphite and preparation method thereof, by weight, each composition ratio of lithium secondary battery anode is: natural spherical plumbago: pitch coke Delanium: additional adhesive SBR: binding agent CMC: aqueous solvent=90: 10: 3.5: 2: 145.The preparation method of cathode size is with embodiment 1, and button cell specific capacity and the test of finished product cycle performance of battery are with embodiment 1.
It is discharge capacity 350mAh/g that table 1 has provided the specific capacity that records negative pole, and 300 times the circulation volume conservation rate is 86.85%, and capacity keeps curve as shown in Figure 3.
Embodiment 4
Another contains lithium secondary battery anode of graphite and preparation method thereof, by weight, each composition ratio of lithium secondary battery anode is: natural spherical plumbago: pitch coke Delanium: additional adhesive SBR: binding agent CMC: aqueous solvent=10: 90: 3.5: 2: 145.The preparation method of cathode size is with embodiment 1, and button cell specific capacity and the test of finished product cycle performance of battery are with embodiment 1.
It is discharge capacity 335mAh/g that table 1 has provided the specific capacity that records negative pole, and 300 times the circulation volume conservation rate is 93.98%, and capacity keeps curve as shown in Figure 4.
Comparative Examples 1
Be the graphite of embodiment 1 preparation in the method for modifying of 01136391.6 disclosed native graphite according to Institute of Chemistry, Academia Sinica's number of patent application, make negative plate and be assembled into battery, test result such as following table 1 by usual technology.
Comparative Examples 2
Adopt native graphite to do negative pole, conductive agent is the SP conductive black, is assembled into battery according to usual prepared negative plate, test result such as following table 1.
Table 1
| Embodiment | Button cell specific capacity (mAh/g) | Button cell is discharging efficiency (%) first | 300 circulation volume conservation rates (%) |
| 1 | 342 | 91％ | 91.23％ |
| 2 | 346 | 91％ | 90.51％ |
| 3 | 350 | 91％ | 86.85％ |
| 4 | 335 | 90％ | 93.98％ |
| Comparative Examples 1 | 317 | 84.55％ | |
| Comparative Examples 2 | 300 | 53.22％ |
No matter as can be seen from the above table, adopt the negative plate and the battery of cathode formula provided by the invention and preparation method preparation, be the button cell specific capacity that adopts the negative pole of the present invention's manufacturing, or finished product battery cycle efficieny is all than prior art height.Therefore, the present invention uses by the collocation of native graphite and Delanium and the preparation method that improves cathode size reaches the purpose that improves native graphite cycle life, effect is very obvious, collocation with native graphite and Delanium simultaneously directly applies to negative pole, the battery production cost has had reduction to a certain degree again, is worth extensive use.
Claims (13)
1. a lithium secondary battery anode that contains graphite is characterized in that: contain native graphite and Delanium.
2. battery cathode according to claim 1, it is characterized in that: by weight, contain: native graphite: Delanium: additional adhesive: binding agent: solvent=10～90: 10～90: 1～10: 1～10: 100～200, native graphite+Delanium=100 wherein.
3. battery cathode according to claim 2 is characterized in that: particle size range 10～30 μ m of described natural graphite particles, described Delanium particle grain size scope 10～30 μ m.
4. battery cathode according to claim 2 is characterized in that: also comprise and be no more than 10 parts conductive agent.
5. battery cathode according to claim 2 is characterized in that: native graphite: Delanium: additional adhesive: binding agent: solvent=50: 50: 2.5: 3.5: 2: 145.
6. according to claim 4 or 5 described battery cathode, it is characterized in that: described native graphite is one or more in sphere, scale or the crystallite shape graphite, described Delanium is all kinds of through high temperature carbonization and graphitized carbon material, and described conductive agent is one or more in natural scale, micro crystal graphite, conductive carbon black or the acetylene black.
7. battery cathode according to claim 6 is characterized in that: bonding agent is CMC or PVDF, and solvent is water or NMP, and when bonding agent was CMC, solvent was a water, and when bonding agent was PVDF, solvent was NMP, and additional adhesive is SBR.
8. a manufacture method that contains the lithium secondary battery anode of graphite comprises the preparation of cathode size, it is characterized in that: the preparation of described cathode size comprises the steps:
The preparation of step 1, binding agent glue: place mixer to stir the 50%-90% of binding agent and total solvent;
Step 2, natural graphite particles and Delanium particle done in de-airing mixer mix, divide 2-3 to criticize then to add the binding agent glue of 10%～80% step 1 preparation and stir;
Step 3, adding additional adhesive butadiene-styrene rubber breast SBR also stir;
The binding agent glue of step 4, the remaining step 1 preparation of adding also stirs;
Step 5, branch 1-3 criticize the remaining solvent of adding and stir;
Step 6, the slurry after step 5 stirred are finished the preparation of natural graphite cathode slurry through vacuumizing, sieving.
9. the described according to Claim 8 manufacture method that contains the lithium secondary battery anode of graphite is characterized in that: also add conductive agent in the step 2, described conductive agent is one or more in natural scale, micro crystal graphite, conductive carbon black or the acetylene black.
10. it is characterized in that according to Claim 8 or the 9 described manufacture methods that contain the lithium secondary battery anode of graphite: described native graphite is one or more in spherical, scale or the crystallite shape graphite.
11. according to Claim 8 or the 9 described manufacture methods that contain the lithium secondary battery anode of graphite, it is characterized in that: described Delanium is all kinds of through high temperature carbonizations and graphitized carbon materials.
12. according to Claim 8 or the 9 described manufacture methods that contain the lithium secondary battery anode of graphite, it is characterized in that: described bonding agent is CMC or PVDF, and solvent is water or NMP, and when bonding agent was CMC, solvent was a water, and when bonding agent was PVDF, solvent was NMP.
13. according to Claim 8 or the 9 described manufacture methods that contain the lithium secondary battery anode of graphite, it is characterized in that: the 50%-90% of total solvent divides 2-5 part to add in batches in the step 1, stirs; Step 2 is that branch 2-3 criticizes the binding agent that adds the preparation of 10%～80% step 1 and stirs; The described stirring of step 3 is that the speed with 1Hz-1000Hz revolution and rotation stirs; The described stirring of step 4 is that branch 1-3 criticizes and adds remaining solvent, after every part of solvent adds, stirs with the speed of 1Hz-1000Hz revolution and rotation; Described the vacuumizing of step 4 is to stir the limit with the revolution of 1Hz-1000Hz speed limit to vacuumize.
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