CN102122709A - Lithium ion battery electrode added with lithium powder, preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery electrode added with lithium powder, preparation method thereof and lithium ion battery Download PDFInfo
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- CN102122709A CN102122709A CN2011100270740A CN201110027074A CN102122709A CN 102122709 A CN102122709 A CN 102122709A CN 2011100270740 A CN2011100270740 A CN 2011100270740A CN 201110027074 A CN201110027074 A CN 201110027074A CN 102122709 A CN102122709 A CN 102122709A
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Abstract
The invention discloses a lithium ion electrode added with lithium powder, and the lithium ion electrode provided by the invention comprises two layers of electrode bodies, wherein the two layers of electrode bodies are roller-pressed together, and a lithium powder layer is closed between the two layers of electrode bodies. The invention further discloses a method for preparing the lithium ion electrode. The invention further discloses a lithium ion battery comprising the lithium ion electrode. When the lithium powder is added into a negative pole, the lithium powder is tightly wrapped between the two layers of electrode bodies, and the problem that the lithium power is separated from the surface of the negative pole and further enters into a positive pole can be avoided; after the lithium powder is shaped between the electrode bodies, the lithium powder is combined into the electrode by a physical method, and the process does not comprise the steps such as solvent dispersion, solvent drying and the like, thereby avoiding the reaction between the lithium powder and a solvent, improving the utilization rate of the lithium powder and also reducing the requirement on the preparation process of the electrode; and a spraying device, a film transfer device and other devices required in the prior art are not required, thereby reducing the manufacturing cost and the process complexity of the electrode.
Description
Technical field
The invention belongs to technical field of chemical power, particularly relate to a kind of lithium ion cell electrode that is added with the lithium powder and preparation method thereof and the lithium ion battery that contains this electrode.
Background technology
Lithium ion battery is the highest battery system of energy density in the present commercialization secondary cell, the commercialization lithium ion battery has good circulation and safety in utilization, it has obtained a large amount of application in fields such as communication, traffic, electronic equipment, industrial products, and obtains bigger market fast.
The important directions of present lithium ion battery exploitation is further to improve the specific energy of battery, mainly passes through the optimization of battery structure and adopts the higher means such as novel electrode material of energy density.Lithium ion battery partly is made up of positive pole, negative pole, electrolyte, barrier film etc. usually.Wherein by cobalt acid lithium, LiMn2O4, tertiary cathode, LiFePO4 etc., negative material has Delanium (as CMS, MCMB etc.) to positive electrode usually usually, and novel silicon series material etc.In battery operated process, lithium ion is at first deviate from by positive pole in charging process and is entered negative pole, is deviate from by negative pole in discharge process then and enters positive pole, and this process also is known as " rocking chair course of reaction ".Find that in the research of lithium ion battery operation principle in the first charge-discharge circulation of lithium ion battery, the decay about 5%～15% can appear in the capacity of positive electrode.Find that after deliberation this is that the surface of negative material and positive electrode all can form the solid electrolyte layer that one deck has protective effect, is also referred to as the SEI film because in initial cyclic process several times.The growth course of this tunic also is the consumption process of lithium ion simultaneously, and lithium ion that is consumed and electrolyte reaction form the SEI film.Though this tunic is useful to the cyclical stability of positive and negative pole material, it also makes the capacity of positive electrode significantly descend simultaneously.Therefore how to reduce or remedy the consumption of lithium ion in the SEI film forming process, be the target that the researcher studies always.
In research in the past, the researcher of U.S. FMC Corp. proposes to add the lithium powder to offset above-mentioned irreversible capacity in lithium ion battery, and the lithium powder dissolves in battery operated process and discharges lithium ion to remedy the lithium ion that is consumed in the SEI film forming process.The result shows that this method has obtained tangible achievement, and the adding of lithium powder can be offset the loss of lithium ion, improves the first charge-discharge efficiency of battery, and then has improved the specific energy of battery.
But, up to the present, the method of the adding lithium powder that FMC proposed does not also obtain large-area use, one of problem of its existence is exactly that the lithium powder adds the technology following several respects problem that has problems: one, the adding of lithium powder, may cause battery uncertain problem to occur, this is because the lithium powder adding method of FMC makes negative terminal surface have a certain amount of lithium powder, and these lithium powder might break away from negative pole in charge and discharge process, and pass barrier film and reach anodal, form the battery micro-short circuit, bring battery capacity to descend or even safety issue; Two, the complex process that FMC proposed, and need special installation.Up to the present, FMC Corp. proposes to add in three kinds of lithium ion battery negatives the method for lithium powder altogether, first kind is that the lithium powder is directly sneaked into cathode size, and by the moulding of common negative pole processes, in this method preparation process the lithium powder can with reactions such as solvent, reduce lithium powder utilance, and processes such as oven dry are had specific (special) requirements; Second method is with spraying process the lithium powder to be sprayed to the negative terminal surface that has prepared, and this method needs special spraying equipment, and technology stability is wayward; The third method is that the lithium powder is prepared film forming in advance, fits to common negative terminal surface then, and this method complex process need additionally increase equipment.
In view of above analysis, several lithium powder application processes that FMC proposed do not obtain promoting all the time.But the thinking of adding the lithium powder in battery is feasible, and has obtained experimental results show that.
Summary of the invention
The present invention provides a kind of lithium ion cell electrode that is added with the lithium powder for solving the technical problem that exists in the known technology, and the lithium powder in this electrode can not break away from electrode, and cost is low; For this reason, the present invention also provides a kind of preparation method of above-mentioned electrode and has contained the lithium ion battery of above-mentioned electrode, and this preparation method can add electrode of lithium cell with the lithium powder easily, realizes the application of lithium powder in lithium ion battery.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is a kind of li-ion electrode that adds the lithium powder, comprises roll-in two-layer electrode body together, is closed with the lithium bisque between the described two-layer electrode body.
The quality of described lithium powder is 10～20% of a described electrode body active material quality.
Second technical scheme that the present invention taked is: a kind of method for preparing above-mentioned li-ion electrode, prepare two layered electrode bodies earlier, again with the roll-in of two layered electrode bodies in the currect collecting net both sides, in the roll-in process, between described two layered electrode bodies, add the lithium powder, obtain adding the li-ion electrode of lithium powder after the roll-in.
The adding quality of described lithium powder is 10～20% of a described electrode body active material quality.
The 3rd technical scheme that the present invention taked is: a kind of lithium ion battery comprises above-mentioned li-ion electrode.
The advantage that the present invention has with good effect is: the method that adds lithium ion cell electrode with existing lithium powder is compared, the present invention has following several respects advantage: when 1) joining the lithium powder in the negative pole, the lithium pruinescence is wrapped between the two-layer electrode body tightly, the lithium powder breaks away from and enter positive pole zone from negative terminal surface problem can not occur; 2) the lithium powder adopts physical method to be attached in the electrode after electrode body is shaped, and this process does not need steps such as solvent dispersion, solvent oven dry, has avoided the reaction between lithium powder and the solvent, has improved the utilance of lithium powder, has reduced the requirement to technology for preparing electrode yet; 3) do not need existing technology devices needed such as spraying equipment, rete transfer apparatus, reduced the manufacturing cost and the process complexity of electrode.
Description of drawings
Fig. 1 is the schematic diagram that prior art coating sizing-agent on matrix forms the stratiform electrode body;
To be that prior art is two-layer form the schematic diagram of negative pole with the electrode body roll-in after matrix separates to Fig. 2 to the copper mesh both sides;
Fig. 3 is the schematic diagram that the present invention adds the lithium powder;
Be added with the lithium ion battery schematic diagram of lithium powder in Fig. 4 negative pole.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, exemplify following examples now, and conjunction with figs. is described in detail as follows:
A kind of lithium ion battery negative that adds the lithium powder comprises roll-in two-layer electrode body together, is closed with the lithium bisque between the two-layer electrode body.
The preparation method of above-mentioned negative pole is: on the basis of existing polymer battery negative pole production method, carry out process modification.The basic production method of present existing polymer battery negative pole is: at first, adopting the graphite-like electrode material is negative electrode active material, adds 1%～30% bonding agent, is mainly copolymerization class binding agent, as the kynar2801:PVDF-HFP copolymer; Binding agent is a solvent with methyl pyrrolidone NMP, adds 0%～30% conductive electrode, and conductive electrode comprises graphite-like conductive agent, unformed conductive black etc.Above material is mixed in ball mill.Be matrix 1 with Copper Foil or PVC plastic film then, the slurry behind the ball milling is applied on the film matrix 1, under 80 ℃～100 ℃ conditions, dry and remove fully, form layered electrode body 2 shown in Figure 1 to solvent.Again with electrode body 2 and matrix 1 careful separation, and utilize roll squeezer with two-layer electrode body roll-in with after matrix separates to the copper mesh both sides, as shown in Figure 2, this has just formed the polymer negative pole, it is a collector with copper mesh 3.
In the present embodiment, in order to realize that the lithium powder joins in the negative pole simply and easily, above technology is improved.Above-mentioned technology with two-layer electrode body roll-in with after matrix separates in the step of copper mesh both sides, between two-layer electrode body, add the lithium powder that has weighed simultaneously, as Fig. 3, the electrode body 2 of copper mesh 3 both sides tightly encases the copper mesh 3 of centre after roll-in, simultaneously also lithium powder 4 is enclosed in the two-layer electrode body 2, finished the adding of lithium powder in negative electrode, the adding quality of lithium powder is 10% of a graphite-like electrode material.The optional artificial plumbago negative pole of using of graphite-like electrode material is as MCMB, CMS etc.
The negative pole main body active material that adopts in the present embodiment is not limited to the graphite-like electrode material, can also be a kind of in the negative material that does not contain lithium that uses in the lithium ion batteries such as silicon series negative material and stannum alloy cathode material, also can be the wherein mixing of at least two kinds of materials.
Can there be the long period in the lithium powder that adopts in the present embodiment through surface passivation under the dry air condition, the particle diameter of lithium powder is at 10um～100um, and the lithium powder generally can obtain by fusion emulsification dispersion method; The addition of lithium powder is determined according to the required lithium ion capacity of battery, is not limited to be 10% of negative pole main body active material, and can also be 20% (mass percent).
Have the prepared anode electrode now with lithium ion battery: with cobalt acid lithium is positive active material, adds 10% conductive agent KS modified graphite, 10% binding agent PVDF Kynoar (being dissolved among the NMP of 10 times of quality).With the aluminium foil is plus plate current-collecting body, adopts rubbing method to obtain laminar anode; Electrode preparation basic process is: above material is mixed with the argon shield ball mill, be applied to then on the aluminium foil, to dry 2h～5h under 80 ℃～100 ℃ conditions, NMP volatilizees fully to solvent, promptly forms anode electrode, places drying box standby in baking oven.
With negative pole and the positive pole of having prepared, cooperate lithium ion battery commodity electrolyte 1M LiPF
6PC: EMC: DMC (1: 1: 1), and lithium ion battery produces three layers of composite diaphragm with Cellgard.Battery adopts the flexible package form, is pack case with the aluminum plastic film.By shown in Figure 4, positive pole 8, negative pole 5, barrier film 7 are packed in the aluminum plastic film pack case, inject electrolyte 6 then and seal, just formed of the present invention and the lithium ion battery of negative pole adding lithium powder.
By add the lithium powder in lithium ion battery negative, after the battery assembling, the lithium powder in the negative pole can generate lithium ion by two kinds of approach.After adding electrolyte in the first battery, the lithium powder can react with the graphite isoreactivity material in the negative material, can form the graphite of embedding lithium state, and these products form both positive and negative polarity with positive pole and react electric right in follow-up charge and discharge process, and can circulate repeatedly; Another kind of mode is, battery discharge for the first time and the after discharge process in, the lithium powder meeting metalloid lithium paper tinsel that adds equally dissolves and discharges lithium ion and enters in the positive active material, and in charging process, graphite isoreactivity material in the preferential and negative material of these lithium ions that produced reacts, can form the graphite of embedding lithium state, these products form both positive and negative polarity with positive pole and react electric right in follow-up charge and discharge process, and can circulate repeatedly.By the addition of control lithium powder, can guarantee that the lithium powder is becoming lithium ion in the discharge for the first time fully, and the lithium powder exists no longer or small amount of residual is only arranged.
The lithium ion battery of forming with this method has higher first charge-discharge efficiency, and higher specific energy.
Similarly, the lithium powder can be joined in the anode electrode equally with same process and to go, but should change copper mesh into aluminium net or nickel screen this moment.The anodal main body active material that adopts can be selected any one positive electrode that uses in the lithium ion batteries such as cobalt acid lithium, LiMn2O4, ternary transition metal material, LiFePO4, phosphoric acid vanadium lithium for use, also can adopt the mixing of at least two kinds of materials in the above-mentioned material.
Corresponding, by in lithium ion cell positive, adding the lithium powder, after the battery assembling, lithium powder in the positive pole can battery charge for the first time and the subsequent charge process in, under high potential the dissolving and discharge lithium ion, lithium ion that these have produced and the graphite isoreactivity material in the negative material react, and can form the graphite of embedding lithium state, these products form both positive and negative polarity with positive pole and react electric right in follow-up charge and discharge process, and can circulate repeatedly.
In like manner, the positive and negative electrode of lithium ion battery all can be and adopts said method to be added with the electrode of lithium powder, and this lithium ion battery can have higher first charge-discharge efficiency equally, and higher specific energy.Its action principle is the same.
In sum, after obtaining to add the negative pole and/or positive pole of lithium powder, cooperate corresponding with it negative or positive electrode, and lithium-ion battery electrolytes, lithium ion battery just can be formed the lithium ion battery that is added with the lithium powder in the complete electrode with parts such as barrier film, casing of lithium ion battery.
Although in conjunction with the accompanying drawings the preferred embodiments of the present invention are described above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away under the scope situation that aim of the present invention and claim protect, can also make a lot of forms, these all belong within protection scope of the present invention.
Claims (5)
1. a li-ion electrode that adds the lithium powder comprises roll-in two-layer electrode body together, it is characterized in that, is closed with the lithium bisque between the described two-layer electrode body.
2. the lithium ion battery negative of adding lithium powder according to claim 1 is characterized in that, the quality of described lithium powder is 10～20% of a described electrode body active material quality.
3. the method for preparing li-ion electrode as claimed in claim 1, prepare two layered electrode bodies earlier, again with the roll-in of two layered electrode bodies in the currect collecting net both sides, it is characterized in that, in the roll-in process, between described two layered electrode bodies, add the lithium powder, obtain adding the li-ion electrode of lithium powder after the roll-in.
4. according to the described method for preparing lithium ion battery negative of claim 3, it is characterized in that the adding quality of described lithium powder is 10～20% of a described electrode body active material quality.
5. a lithium ion battery is characterized in that, comprises li-ion electrode as claimed in claim 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103021675A (en) * | 2012-12-30 | 2013-04-03 | 万裕三信电子(东莞)有限公司 | Lithium ion capacitor and negative electrode plate thereof and manufacturing method of negative electrode plate |
| CN103035952A (en) * | 2012-12-26 | 2013-04-10 | 东莞新能源科技有限公司 | Injection method of lithium ion battery electrolyte |
| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN105336914A (en) * | 2014-07-01 | 2016-02-17 | 宁德时代新能源科技有限公司 | Lithium ion secondary battery and lithium-rich negative plate thereof |
| CN107732153A (en) * | 2017-10-10 | 2018-02-23 | 江西创迪科技有限公司 | A kind of lithium ion battery two-layer compound iron phosphate lithium electrode |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103035952A (en) * | 2012-12-26 | 2013-04-10 | 东莞新能源科技有限公司 | Injection method of lithium ion battery electrolyte |
| CN103035952B (en) * | 2012-12-26 | 2016-12-28 | 东莞新能源科技有限公司 | A kind of injection method of lithium ion battery electrolyte |
| CN103021675A (en) * | 2012-12-30 | 2013-04-03 | 万裕三信电子(东莞)有限公司 | Lithium ion capacitor and negative electrode plate thereof and manufacturing method of negative electrode plate |
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| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN105336914A (en) * | 2014-07-01 | 2016-02-17 | 宁德时代新能源科技有限公司 | Lithium ion secondary battery and lithium-rich negative plate thereof |
| CN105336914B (en) * | 2014-07-01 | 2018-07-13 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery and lithium-rich negative plate thereof |
| CN107732153A (en) * | 2017-10-10 | 2018-02-23 | 江西创迪科技有限公司 | A kind of lithium ion battery two-layer compound iron phosphate lithium electrode |
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Application publication date: 20110713 |