CN101640264A - Method for manufacturing negative pole piece of lithium-ion battery and lithium-ion battery using negative pole piece - Google Patents
Method for manufacturing negative pole piece of lithium-ion battery and lithium-ion battery using negative pole piece Download PDFInfo
- Publication number
- CN101640264A CN101640264A CN200810029767A CN200810029767A CN101640264A CN 101640264 A CN101640264 A CN 101640264A CN 200810029767 A CN200810029767 A CN 200810029767A CN 200810029767 A CN200810029767 A CN 200810029767A CN 101640264 A CN101640264 A CN 101640264A
- Authority
- CN
- China
- Prior art keywords
- pole piece
- ion battery
- lithium
- slurry
- lithium ion
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides a method for manufacturing a negative pole piece of a lithium-ion battery, which comprises the following steps: (1) mixing polyvinylidene fluoride (PVDF) and graphite in an NMPsolvent and uniformly stirring the mixture to make slurry; (2) drying the mixed slurry to form powder; (3) stirring processed powder in a water-base system of CMC-SBR; (4) grinding the slurry till thegranularity of the slurry meets requirements for coating; and (5) evenly coating the processed slurry on a copper foil and obtaining the negative pole piece after drying. A lithium-ion battery manufactured by using the negative pole piece has excellent low temperature circulation performance and ensures the stability of high temperature circulation and the wide use of lithium ions.
Description
Technical field
The present invention relates to a kind of lithium ion battery cathode pole piece manufacture method and use the lithium ion battery of this cathode pole piece, refer in particular to a kind of graphite powder of handling through special modification of using and make the method for negative plate as negative electrode active material and with the lithium ion battery of this cathode pole piece making.
Background technology
When existing opportunity, the lithium ion battery industry also faces huge challenge, battery safety, and low temperature is analysed lithium, and high temperature expands or the like, and the solution that demands perfection urgently proposes.For example, the lithium ion battery user has strict requirement to low temperature, and as 5 ℃, 10 ℃ require circulation good, the lithium phenomenon can not occur analysing, and 45 degree discharge and recharge with 60 degree hot conditionss and also do not allow battery flatulence simultaneously.
Graphite has obtained using widely and development fully as the negative material of lithium ion battery.Be accompanied by the continuous expansion of application, constantly widening of application conditions also had higher requirement for the environment for use of lithium ion battery, the condition that discharges and recharges.Graphite material is mainly used in water-based system (CMC-SBR, sodium carboxymethylcellulose-butadiene-styrene rubber) and two kinds of systems of oiliness (PVDF, Kynoar) system as the negative material of lithium ion battery at present.
We discharge and recharge by the water base negative electrode lithium ion battery of traditional usefulness at low temperatures, because the negative pole of CMC-SBR system, when forming SEI (Solid Electrolyte Interface) film, impedance is bigger, and performance is more obvious at low temperatures; In addition, CMC-SBR itself also is a kind of colloid of not leading lithium ion, and is also bad to the wettability of electrolyte, the comprehensive function of these factors, make it when low temperature charges, the sub-ability variation of the wettability of electrolyte and diversion, there is serious potential safety hazard in such battery.
Analyse the lithium problem in order to solve low temperature, conventional batteries generally adopts PVDF base negative pole, and in this system, the SEI film that forms in negative terminal surface is more loose, and impedance is less, is beneficial to the embedding of taking off of the infiltration of electrolyte and lithium ion.The method has solved the circulation of battery low temperature substantially and has analysed lithium, but because PVDF at high temperature easily expands, cause the battery distortion, and the security performance of battery (as drift bolt, tests such as short circuits) is relatively poor.
To sum up, concerning the cathode of lithium battery of CMC-SBR system, advantage such as it shows good normal temperature and high-temperature behavior, and is environmentally friendly, and fail safe is better, but its low temperature cycle performance is relatively poor, occurs analysing the lithium phenomenon easily, and the risk that may cause safety problem increases; To the negative pole of PVDF matrix system, it shows excellent low-temperature characteristics, even 5 degree 1C/1C circulations do not have separating out of lithium metal yet, but its high temperature circulation is prone to and analyses the lithium phenomenon, and electric core easy deformation, and it is bigger to expand, and fail safe is bad.Like this, traditional lithium ion battery is difficult to accomplish taking into account of high temperature performance and fail safe.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, by the new graphite modified processing method and the optimization process of technology, under the prerequisite that does not reduce fail safe, not only obtained good low temperature cycle performance, and guaranteed its cyclical stability of 60 ℃, for lithium ion more the application of broad range assurance is provided.
For achieving the above object, technical scheme provided by the invention is as follows: a kind of lithium ion battery, it partly is made up of both positive and negative polarity pole piece, barrier film, electrolyte, pack case etc.Material that lithium ion battery used and the traditional handicraft that the present invention relates to are basic identical, just in advance graphite are carried out PVDF and coat processing, and concrete technology is as follows:
1, PVDF with evenly stir into slurry after graphite mixes in NMP (N-methyl pyrrolidone) solvent;
2, mixed slurry is dried to powder;
3, the powder after the processing stirs in the aqueous based systems of CMC-SBR;
4, slurry ground make granularity reach the requirement of coating.
To be uniformly coated on through the slurry of above-mentioned processing on the Copper Foil then, obtain cathode pole piece after the drying.Make anode slice of lithium ion battery by traditional handicraft again, after above-mentioned positive plate, barrier film and cathode pole piece superposeed successively, make battery, and battery is packed in the battery packages shell by lamination or winding process, in it, inject electrolyte, after operation such as changing into, make battery.
The present invention is based on above understanding,, carry out the water base material that stirs with the graphite powder after this processing again, coating by coat one deck PVDF earlier in the graphite powder surface to water base negative pole (CMC/SBR) and PVDF base negative pole high temperature performance.Utilize the made lithium ion battery of the technology of the present invention, except that having good high low temperature cycle performance, also have reliable security performance.
Marginal data
Fig. 1 charges with 0.8C in the time of 5 ℃ for lithium ion battery of the present invention, the cyclic curve during the 0.5C discharge.
Fig. 2 charges with 1C in the time of 25 ℃ for lithium ion battery of the present invention, the cyclic curve during the 1C discharge.
Fig. 3 charges with 1C in the time of 60 ℃ for lithium ion battery of the present invention, the cyclic curve during the 1C discharge.
Embodiment
Material that lithium ion battery used and the traditional handicraft that the present invention relates to are basic identical, just for guaranteeing the high temperature performance and the fail safe of battery simultaneously, need in advance graphite to be carried out PVDF and coat processing, and concrete technology is as follows:
Get a certain amount of PVDF and be dissolved in nmp solvent, form the solution that clarification and concentration are about 8%-10%.After treating stirring, dissolving fully, the graphite powder is added in the above-mentioned mixed solution, the mass ratio range of PVDF binding agent and graphite powder can be 0.5-5: 95-99.5, preferred 1-3: 97-99 after this experimental example is waited to stir, removes the NMP evaporation, the powder oven dry after handling, the graphite powder that finally obtains, 120 ℃ of further dry 24h in baking oven obtain coating the graphite of handling through PVDF.
Re-use the above-mentioned graphite that coats processing through PVDF as battery cathode active substance, make battery through traditional handicraft, concrete steps are as follows:
Cathode pole piece preparation: will coat graphite, Super-P (conductive carbon black), the CMC (water based adhesive of handling through PVDF, carboxymethyl cellulose), SBR (Styrene Butadiene Rubber, a kind of rubber) be 95.5: 1.5 according to mass ratio:: add NMP (N-methyl pyrrolidone) at 1.5: 1.5 and mix and stir and obtain having the slurry of certain flowability, again above-mentioned slurry is coated in the two sides of the thick metal copper foil of 9um, is dried into cathode pole piece with certain flexibility.Then through colding pressing, itemize (promptly to cut out, cut into the size of required size through cathode pole piece), will be connected on the Copper Foil with the negative lug that the thick copper sheet of 0.4mm is made again after, make cathode pole piece.
Anode pole piece preparation: is to add NMP at 95.5: 2.2: 2.3 to mix and stir and obtain having the slurry of certain flowability with LiCoO2 (cobalt acid lithium), Super-P, PVDF according to mass ratio, be coated in the two sides of the thick metal aluminum foil of 16um, be dried into anode pole piece with certain pliability.Then through colding pressing, itemize, will be connected on the aluminium foil with the positive pole ear that the thick aluminium flake of 0.4mm is made again and make anode pole piece.
The anode pole piece of making, cathode pole piece and barrier film are made naked electric core by lamination or coiling, barrier film can adopt polypropylene (PP)-polyethylene (PE)-three layers of laminated film of polypropylene PP, then battery is packed in the battery packages shell, in it, inject electrolyte, with lithium hexafluoro phosphate (LiPF
6) be lithium salts, the ethylene carbonate with 20%, 30% methyl ethyl carbonate and 50% dimethyl carbonate are solvent, through changing into, technologies such as ageing make finished product electricity core again.
The lithium ion battery that makes is as stated above carried out volume test, and test result is referring to table 1.
Table 1
| The test sequence number | Temperature (℃) | The charge/discharge multiplying power | The charge and discharge cycles number of times | Capability retention |
| ??1 | ??5 | ??0.8C/0.5C | ??18 | ??94％ |
| ??2 | ??10 | ??0.7C/0.5C | ??300 | ??92％ |
| ??3 | ??14 | ??0.7C/0.5C | ??60 | ??96％ |
| ??4 | ??25 | ??1C/1C | ??1000 | ??92％ |
| ??5 | ??45 | ??1C/1C | ??500 | ??94％ |
| ??6 | ??60 | ??1C/1C | ??340 | ??93％ |
Please associative list 1 referring to Fig. 1 to Fig. 3, as can be seen from Figure 1, lithium ion battery of the present invention in the time of 5 ℃, with the 0.8C charging, the 0.5C discharge, after 18 circulations, capability retention is also 94%.As can be seen from Figure 2, lithium ion battery of the present invention is in the time of 25 ℃, and with the 1C charging, 1C discharges, and process is through 1000 circulations, and capability retention is also more than 92%.As Fig. 3 as can be seen, the lithium ion battery of invention is in the time of 60 ℃, and with the 1C charging, 1C discharges, and process is through 340 circulations, and capability retention is also more than 93%.
Utilize the made lithium ion battery of the technology of the present invention, except that having good high low temperature cycle performance, also have reliable security performance, our experiments show that lithium does not all appear analysing in its high low temperature circulation, and high temperature (60 ℃) circulation time bulge phenomenon can not occur yet.So, the present invention is by coating one deck PVDF in the graphite powder surface, carry out the water base material that stirs with the graphite powder after this processing again, coating, pass through the lithium ion battery that traditional handicraft is made again, can obviously improve the low temperature of battery and analyse lithium, suppress high temperature and expand, and obtain better electrochemical performance and security performance.
Need to prove, the announcement of book and instruction according to the above description, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention equivalent modifications more of the present invention and change.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (4)
1, a kind of method of making the cathode pole piece of lithium ion battery, it comprises the steps:
(1) PVDF with evenly stir into slurry after the graphite powder mixes in nmp solvent;
(2) mixed slurry is dried to powder;
(3) powder after the processing stirs in the aqueous based systems of CMC-SBR;
(4) slurry is ground make granularity reach the requirement of coating;
(5) will be uniformly coated on through the slurry of above-mentioned processing on the Copper Foil then, obtain cathode pole piece after the drying.
2, a kind of method of making the cathode pole piece of lithium ion battery as claimed in claim 1 is characterized in that: the mass ratio range of PVDF and graphite powder is 0.5-5: between the 95-99.5.
3, a kind of method of making the cathode pole piece of lithium ion battery as claimed in claim 1 is characterized in that: the mass ratio range of PVDF and graphite powder is 1-3: between the 97-99.
4, a kind of lithium ion battery, it be is characterized in that by both positive and negative polarity pole piece, barrier film, electrolyte and pack case: cathode pole piece is to adopt the method in the claim 1 or 2 or 3 to make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810029767A CN101640264A (en) | 2008-07-28 | 2008-07-28 | Method for manufacturing negative pole piece of lithium-ion battery and lithium-ion battery using negative pole piece |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810029767A CN101640264A (en) | 2008-07-28 | 2008-07-28 | Method for manufacturing negative pole piece of lithium-ion battery and lithium-ion battery using negative pole piece |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101640264A true CN101640264A (en) | 2010-02-03 |
Family
ID=41615153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810029767A Pending CN101640264A (en) | 2008-07-28 | 2008-07-28 | Method for manufacturing negative pole piece of lithium-ion battery and lithium-ion battery using negative pole piece |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101640264A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005562A (en) * | 2010-09-30 | 2011-04-06 | 东莞新能源科技有限公司 | Lithium ion battery and manufacturing method thereof |
| CN102623702A (en) * | 2012-03-19 | 2012-08-01 | 宁德新能源科技有限公司 | Li-ion battery as well as cathode plate and preparation method thereof |
| US20130034651A1 (en) * | 2011-08-03 | 2013-02-07 | Hilmi Buqa | Aqueous Slurry For Battery Electrodes |
| CN103918108A (en) * | 2011-10-05 | 2014-07-09 | 加州大学校务委员会 | Lithium metal doped electrodes for lithium-ion rechargeable chemistry |
| US20150303521A1 (en) * | 2012-11-20 | 2015-10-22 | Nec Corporation | Lithium ion secondary battery |
| CN102290577B (en) * | 2011-07-25 | 2016-03-23 | 东莞新能源科技有限公司 | A kind of negative pole of lithium ion battery |
| EP2631974B1 (en) | 2012-02-21 | 2016-07-27 | Samsung SDI Co., Ltd. | Lithium battery |
| US9905887B2 (en) | 2012-06-05 | 2018-02-27 | Nec Corporation | Lithium secondary battery |
| CN109888173A (en) * | 2019-02-26 | 2019-06-14 | 天津工业大学 | The preparation method of three-dimensional continuous poriferous copper/graphite electrode |
| CN112098875A (en) * | 2020-08-27 | 2020-12-18 | 广州汽车集团股份有限公司 | Lithium ion battery lithium analysis detection method |
-
2008
- 2008-07-28 CN CN200810029767A patent/CN101640264A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005562B (en) * | 2010-09-30 | 2013-02-27 | 东莞新能源科技有限公司 | Lithium ion battery and manufacturing method thereof |
| CN102005562A (en) * | 2010-09-30 | 2011-04-06 | 东莞新能源科技有限公司 | Lithium ion battery and manufacturing method thereof |
| CN102290577B (en) * | 2011-07-25 | 2016-03-23 | 东莞新能源科技有限公司 | A kind of negative pole of lithium ion battery |
| US11283078B2 (en) | 2011-08-03 | 2022-03-22 | Leclanche' S.A. | Aqueous slurry for battery electrodes |
| US20130034651A1 (en) * | 2011-08-03 | 2013-02-07 | Hilmi Buqa | Aqueous Slurry For Battery Electrodes |
| US9444090B2 (en) * | 2011-10-05 | 2016-09-13 | The Regents Of The University Of California | Lithium metal doped electrodes for lithium-ion rechargeable chemistry |
| CN103918108A (en) * | 2011-10-05 | 2014-07-09 | 加州大学校务委员会 | Lithium metal doped electrodes for lithium-ion rechargeable chemistry |
| US20140227432A1 (en) * | 2011-10-05 | 2014-08-14 | The Regents Of The University Of California | Lithium metal doped electrodes for lithium-ion rechargeable chemistry |
| CN103918108B (en) * | 2011-10-05 | 2017-05-10 | 加州大学校务委员会 | Lithium metal doped electrodes for lithium-ion rechargeable chemistry |
| EP2631974B2 (en) † | 2012-02-21 | 2019-08-21 | Samsung SDI Co., Ltd. | Lithium battery |
| EP2631974B1 (en) | 2012-02-21 | 2016-07-27 | Samsung SDI Co., Ltd. | Lithium battery |
| CN102623702B (en) * | 2012-03-19 | 2014-07-23 | 宁德新能源科技有限公司 | Li-ion battery as well as cathode plate and preparation method thereof |
| CN102623702A (en) * | 2012-03-19 | 2012-08-01 | 宁德新能源科技有限公司 | Li-ion battery as well as cathode plate and preparation method thereof |
| US9905887B2 (en) | 2012-06-05 | 2018-02-27 | Nec Corporation | Lithium secondary battery |
| US20150303521A1 (en) * | 2012-11-20 | 2015-10-22 | Nec Corporation | Lithium ion secondary battery |
| US10177413B2 (en) * | 2012-11-20 | 2019-01-08 | Nec Corporation | Lithium ion secondary battery |
| CN109888173A (en) * | 2019-02-26 | 2019-06-14 | 天津工业大学 | The preparation method of three-dimensional continuous poriferous copper/graphite electrode |
| CN109888173B (en) * | 2019-02-26 | 2021-09-17 | 天津工业大学 | Preparation method of three-dimensional continuous porous copper/graphite electrode |
| CN112098875A (en) * | 2020-08-27 | 2020-12-18 | 广州汽车集团股份有限公司 | Lithium ion battery lithium analysis detection method |
| CN112098875B (en) * | 2020-08-27 | 2023-08-11 | 广汽埃安新能源汽车有限公司 | Method for detecting lithium ion battery lithium precipitation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101640264A (en) | Method for manufacturing negative pole piece of lithium-ion battery and lithium-ion battery using negative pole piece | |
| CN102956895B (en) | Positive electrode that surface recombination is coated and preparation method thereof and lithium ion battery | |
| CN105742641A (en) | Conductive coating and lithium-ion battery employing same | |
| CN107403904B (en) | Lithium ion battery and negative plate thereof | |
| CN105958008A (en) | Composite positive electrode plate of lithium ion battery, preparation method thereof and lithium ion battery | |
| CN101867037A (en) | Iron-phosphate-based lithium-ion battery positive plate and preparation method thereof | |
| CN102881861A (en) | High-temperature lithium ion battery anode slice | |
| JP5530851B2 (en) | Method for producing electrode of lithium ion secondary battery and method for producing lithium ion secondary battery | |
| CN103606703A (en) | Lithium ion battery with uniform and stable current density | |
| CN102332561A (en) | Manufacturing method for lithium ion battery pole piece | |
| CN112151736A (en) | Preparation method of pole piece with coating and lithium ion battery | |
| CN109904374A (en) | A kind of anti-overcharge diaphragm and its preparation method and application | |
| CN111048749B (en) | Negative pole piece, lithium ion battery and manufacturing method thereof | |
| CN104134779A (en) | High voltage lithium ion battery positive pole piece and preparation method thereof | |
| CN107959021A (en) | A kind of preparation method of cylinder nickle cobalt lithium manganate power battery | |
| CN102623702B (en) | Li-ion battery as well as cathode plate and preparation method thereof | |
| CN102290566B (en) | Lithium battery anode preparing method and lithium battery | |
| KR20150087864A (en) | Electrode binder composition for controlling the drying rate, the electrode and lithium secondary cell comprising the same | |
| CN111916835B (en) | Polymer lithium ion battery and preparation method thereof | |
| CN108987705B (en) | Electrode material composition, lithium ion battery positive plate and lithium ion battery | |
| CN105406029A (en) | Preparation method of lithium-ion battery positive pole piece or negative pole piece | |
| CN105355854A (en) | Fabrication method of positive plate for high-energy-density lithium-ion battery | |
| CN101071847A (en) | High power lithiumion cell positive electrode and its manufacturing method | |
| CN116314600A (en) | Pole piece and battery | |
| CN103490042A (en) | Lithium ion battery negative pole piece, making method thereof, and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100203 |