CN101127395A - A lithium secondary battery cathode and its making method - Google Patents
A lithium secondary battery cathode and its making method Download PDFInfo
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- CN101127395A CN101127395A CNA2006100621290A CN200610062129A CN101127395A CN 101127395 A CN101127395 A CN 101127395A CN A2006100621290 A CNA2006100621290 A CN A2006100621290A CN 200610062129 A CN200610062129 A CN 200610062129A CN 101127395 A CN101127395 A CN 101127395A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 25
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 49
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006257 cathode slurry Substances 0.000 claims description 5
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- 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
- 239000008187 granular material Substances 0.000 claims description 3
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- 238000007873 sieving Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 4
- 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
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
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- 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
- 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 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 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
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- 229910052709 silver Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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Images
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The utility model discloses a cathode of lithium secondary battery, which is characterized in that the components are as following according to the weight: natural graphite: conductive agent: auxiliary agglomerant: agglomerant: solvent is equal to 100:1 to 10:1 to 10:1 to 10:100 to 200; the grain size range of the graphite grain is 10 to 30Mum and the grain size range of the conductive agent is 1 to 30Mum; wherein the natural graphite is spherical, flake or microcrystalline graphite and the conductive agent is natural flack, microcrystalline graphite, conductive carbon black or acetylene black. The utility model also discloses the manufacture method of the cathode of lithium secondary battery, which overcomes the shortcomings in the prior art that the net natural graphite needs to be coated and modified before imported to the cathode system of the lithium-ion battery; thus the utility model has the advantages that the method enhances the cycle life of the natural graphite by optimizing the application prescription of the natural graphite and the preparation method of the natural graphite cathode sizing agent, meanwhile the production cost of the battery is reduced.
Description
Technical field
The present invention relates to lithium secondary battery and make the field, be specifically related to lithium secondary battery anode and manufacture method thereof.
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 whippy SEI film on its surface, 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 reported at graphite surface and plated layer of metal film by vacuum, as: Ag, Au, Bi, In, Pb, Pd, Sn, Zn etc.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.Its principle is it on the one hand is thereby that these metals can form alloy with lithium ion but do not hinder the migration raising capacity of lithium ion; Be that the metal film that plates has changed charcoal negative terminal surface SEI film formation mechanism on the other hand.
A large amount of research has also been done for the modification of native graphite by domestic many manufacturers, Institute of Chemistry, Academia Sinica discloses the method for modifying that a kind of patent No. is 0113639.6 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, and 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 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, by weight, contain: native graphite: conductive agent: additional adhesive: binding agent: solvent=100: 1～10: 1～10: 1～10: 100～200, graphite granule particle size range 10～30 μ m, 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.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.
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 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 preparation of natural graphite cathode slurry through vacuumizing, sieving.
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.
Native graphite can be sphere, scale, crystallite shape graphite in the above-mentioned steps, and conductive agent can be natural scale or micro crystal graphite and conductive carbon black or 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 reaches the purpose that improves native graphite cycle life by the application prescription of optimization native graphite and the preparation method of natural graphite cathode slurry, and effect is very obvious.And, directly native graphite is applied to the production cost that battery helps reducing battery.
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 2 batteries.
Embodiment
Embodiment 1
A kind of lithium secondary battery anode and preparation method thereof, by weight, the formula rate of lithium secondary battery anode is: natural spherical plumbago: natural flake graphite conductive agent: additional adhesive SBR: binding agent CMC: aqueous solvent=100: 2.5: 3.5: 2: 145, and the particle size range 18-20 μ m of natural spherical plumbago wherein.Graphite granule particle size range 10～30 μ m, natural flake graphite conductive agent particle size range 1～30 μ m.
The preparation method of cathode size:
1) preparation binding agent glue: at first in binding agent CMC, add 28% of aqueous solvent, (can be the mixer of eggbeater or other type) stirs in mixer, mixing time is 40 minutes, and then 20% continuation that adds aqueous solvent is stirred, mixing time is 10 minutes, add 32% of solvent at last and stir, mixing time is 10 minutes, finishes preparation binding agent glue process.
2) preparation slurry: natural spherical plumbago particle and natural flake graphite conductive agent were 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 (in batches adding in order to prevent two kinds of binding agent bag groups) 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 native graphite specific capacity is made negative plate with the cathode size coating of preparation, and electrolyte is 1mol/1LiF
6PO
4EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) (1: 1: 1), metal lithium sheet is to electrode, is assembled into the specific capacity of the natural graphite cathode of button cell test preparation.
Other arrange in pairs or groups positive plate of LiCoO2 preparation, electrolyte is 1M LiF
6PO
4Three component mixed solvent EC: DMC: EMC=1: 1: 1, adopt commercial micro-pore septum to be assembled into the finished product battery, discharge and recharge experiment with the speed of 1C, discharging and recharging deboost is 4.2V～3V, the circulation conservation rate C300/C1 that test battery is 300 times, test result as shown in Figure 1.It is that 351mAh/g and 300 circulation volume conservation rates are 85.83% that table 1 provides the button cell specific capacity.
Embodiment 2
Another kind of lithium secondary battery anode and preparation method thereof, by weight, the formula rate of lithium secondary battery anode is: natural spherical plumbago: natural flake graphite conductive agent: additional adhesive SBR: binding agent CMC: aqueous solvent=100: 2.5: 4: 2: 145, and the particle size range 18-20 μ m of natural spherical plumbago wherein.The preparation process of cathode size is with embodiment 1, and button cell specific capacity and the test of finished product cycle performance of battery are with 1,300 circulation volume conservation rate of embodiment result as shown in Figure 2.
Embodiment 3
Another lithium secondary battery anode and preparation method thereof, by weight, the formula rate of lithium secondary battery anode is: natural spherical plumbago: acetylene black conductive agent: additional adhesive SBR: binding agent CMC: aqueous solvent=100: 2.5: 4: 2: 145, and the particle size range 18-20 μ m of natural spherical plumbago wherein.The preparation process of cathode size is with embodiment 1, and button cell specific capacity and the test of finished product cycle performance of battery are with 1,300 circulation volume conservation rate of embodiment result as shown in Figure 3.
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 carbon black, is assembled into battery according to usual prepared negative plate, test result such as following table 1.
| Embodiment | Button cell specific capacity (mAh/g) | Button cell is discharging efficiency (%) first | 300 circulation volume conservation rates (%) |
| 1 | 351 | 91％ | 85.83％ |
| 2 | 348 | 92％ | 86.76％ |
| 3 | 342 | 91％ | 87.81％ |
| Comparative Examples 1 | 317 | 84.55％ | |
| Comparative Examples 2 | 300 | 53.22％ |
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, no matter the button cell specific capacity and the first charge-discharge efficiency of negative pole, still the finished product battery cycle efficieny made from the present invention is all than prior art height, invention reaches the purpose that improves native graphite cycle life by the application prescription of optimization native graphite and the preparation method of natural graphite cathode slurry, effect is very obvious, is worth extensive use.
Claims (10)
1. a lithium secondary battery anode by weight, contains following component: native graphite: conductive agent: additional adhesive: binding agent: solvent=100: 1～10: 1～10: 1～10: 100～200.
2. battery cathode according to claim 1 is characterized in that: described native graphite is sphere, scale or crystallite shape graphite, and described conductive agent is natural scale, micro crystal graphite, conductive carbon black or acetylene black.
3. battery cathode according to claim 2 is characterized in that: native graphite: conductive agent: additional adhesive: binding agent: solvent=100: 2.5: 4: 2: 145.
4. according to any described battery cathode of claim 1-3, it 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.
5. according to any described battery cathode of claim 1-3, it is characterized in that: the particle size range of graphite granule is 10～30 μ m, and the particle size range of conductive agent is 1～30 μ m.
6. the manufacture method of a lithium secondary battery anode 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 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 preparation of natural graphite cathode slurry through vacuumizing, sieving.
7. the manufacture method of a kind of lithium secondary battery anode according to claim 6, it is characterized in that: native graphite is one or more in sphere, scale or the crystallite shape graphite in the step 2, and conductive agent is one or more in natural scale, micro crystal graphite, conductive carbon black or the acetylene black.
8. the manufacture method of a kind of lithium secondary battery anode according to claim 6, 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.
9. the manufacture method of a kind of lithium secondary battery anode according to claim 6, it is characterized in that: the 50%-90% of total solvent divides 2-5 part in the step 1, adds in batches, stirs.
10. the manufacture method of a kind of lithium secondary battery anode according to claim 4 is characterized in that: 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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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088077A (en) * | 2010-12-25 | 2011-06-08 | 东莞市良源电池科技有限公司 | Preparation method of cathode of lithium ion battery |
| CN102569733A (en) * | 2010-12-21 | 2012-07-11 | 比克国际(天津)有限公司 | Preparation method for lithium ion battery slurry, as well as battery slurry and lithium ion battery |
| CN102598370A (en) * | 2009-08-13 | 2012-07-18 | Snu研发业务基金会 | Amorphous anode active material, preparation method of electrode using same, secondary battery containing same, and hybrid capacitor |
| CN102891283A (en) * | 2011-07-22 | 2013-01-23 | 湖北骆驼特种电源有限公司 | Dry blending process for cathode of lithium-ion power battery |
| CN103117392A (en) * | 2013-02-27 | 2013-05-22 | 江苏乐能电池股份有限公司 | Slurry compounding process of lithium ion battery slurry |
| CN103262306A (en) * | 2010-12-17 | 2013-08-21 | 艾利电力能源有限公司 | Negative electrode for non-queous electrolyte secondary battery, non-aqueous electrolyte secondary battery and production method for negative electrode for non-aqueous electrolyte secondary battery |
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2006
- 2006-08-15 CN CNA2006100621290A patent/CN101127395A/en active Pending
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| CN109997253B (en) * | 2016-12-08 | 2022-07-22 | 松下知识产权经营株式会社 | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
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