CN105655646A - Lithium ion energy storage element and manufacturing method thereof - Google Patents
Lithium ion energy storage element and manufacturing method thereof Download PDFInfo
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Abstract
The present invention provides a lithium ion energy storage element, which comprises: a positive electrode, wherein the positive electrode comprises a first current collection sheet and a positive electrode active material on the first current collection sheet; a negative electrode, wherein the negative electrode comprises a second current collection sheet and a negative electrode active material on the second current collection sheet, and the negative electrode active material is selected from a group comprising a carbon-containing material, a Si alloy and a Sn alloy; and an electrolyte, wherein the positive electrode active material comprises a lithium ion provider and a positive electrode frame active material, and the lithium ion provider is lithium peroxide, lithium oxide, or a mixture of lithium peroxide and lithium oxide. The present invention further relates to a manufacturing method of the lithium ion energy storage element.
Description
Technical field
The present invention is relevant with lithium-ion energy storage element, is particularly to positive active material and comprises lithium ion supplier and the lithium-ion energy storage element of positive pole framework active substance.
Background technology
In numerous energy storage technologies, lithium ion battery due to have energy density big, have extended cycle life, weight is light, the advantage such as pollution-free, be considered as the next generation and efficiently can take formula chemical power source. The aspects such as digital camera, smart mobile phone, notebook computer it are widely used at present. Along with the further lifting of lithium ion battery energy density, its Application Areas expands. Along with mobile electronic equipment to heavy body, long-life batteries demand growing, the performance of lithium ion battery is had higher requirement by people.
Lithium ion battery comprises negative pole, ionogen and positive pole usually. The positive active material of lithium ion battery not only participates in electrochemical reaction as electrode materials, and can be used as lithium source, and positive active material normally embeds lithium metal oxide wherein containing lithium atom. Lithium metal oxide conventional in existing market is cobalt acid lithium, lithium nickelate and lithium manganate etc. But, above-mentioned lithium metal oxide is after repeating discharge and recharge, and none can show the appropriately combined characteristic of high initial electrical capacity, high thermal stability and good electrical capacity maintenance.
Lithium ion battery is limited to the specific capacitance amount of its positive pole lithium metal oxide, and cannot show high specific capacitance amount. Therefore, if to be improved the specific capacitance amount of lithium cell, it is necessary to increase the source of lithium. The general practice coats negative pole using lithium metal uniformly as lithium source, or is plated on negative pole in the way of the 3rd pole, and due to lithium metal very active, very difficult being not easy performs above two kinds of engineering methods, also is not easy to be uniformly distributed simultaneously.
Owing to lithium metal has the shortcoming such as security and stability, therefore current business-like lithium-ion secondary cell can only use the positive electrode material containing lithium ion and the negative material that can store lithium ion as work system. Due in recent years, energy demand fast lifting, the energy density of lithium-ion secondary cell is bound to promote again, and especially positive electrode material can say it is the core of whole battery. But, the stability that is limited in cathode material structure and lithium ion can embedding go out amount, the lifting of gram electrical capacity has reached bottleneck.
It has been proposed that some materials such as FeF3��FePO4And V2O5Deng, they have good electrical capacity and higher platform voltage, are the candidate materials promoting energy density. But but must not arrange in pairs or groups with lithium metal containing lithium ion for fear of itself, it is only applicable to half-cell test, cannot be used in full battery, limit the selectivity of positive electrode material.
Summary of the invention
In order to solve the problems of the technologies described above, the present invention provides a kind of lithium-ion energy storage element, comprises lithium ion supplier and the positive active material of positive pole framework active substance by use, can show high specific capacitance amount.
A kind of lithium-ion energy storage element provided by the invention, comprising:
One positive pole, its positive active material comprising one first collection electricity sheet and being positioned on this first collection electricity sheet;
One negative pole, its negative electrode active material comprising one the 2nd collection electricity sheet and being positioned on the 2nd collection electricity sheet, this negative electrode active material is selected from the group being made up of a carbonaceous material, Si alloy and Sn alloy; And
One ionogen, between this positive pole and this negative pole, wherein this positive active material comprises a lithium ion supplier and a positive pole framework active substance, and this lithium ion supplier is lithium peroxide, Lithium Oxide 98min or both mixtures.
Preferably, this positive pole framework active substance of this positive active material is selected from the group being made up of anatase phase titanium dioxide, carbon-sulfur compound, carbonaceous material and fluorocarbon material.
Preferably, the sulphur carbon ratio example of the carbon-sulfur compound of this positive pole framework active substance is 5 ~ 7:3 ~ 5.
Preferably, this positive pole framework active substance is lithium metal oxide.
Preferably, this positive active material more comprises a conductive carbon, and this conductive carbon is superP carbon black, KS6 graphite or both combinations.
The present invention also provides the manufacture method of a kind of lithium-ion energy storage element, comprises following step:
A lithium ion supplier, positive pole framework active substance and tackiness agent are mixed by () respectively with certain weight ratio, and be incorporated in and a dispersion agent prepares positive active material, wherein this lithium ion supplier is lithium peroxide, Lithium Oxide 98min or both mixtures;
B this positive active material is applied to an aluminium foil film forming by () after, coated electrode is dried, thus prepares positive pole; And
C () uses this positive pole preparing gained, the negative pole with negative electrode active material and is folded in a porousness barrier film wherein, injected by ionogen between this positive pole and this negative pole, thus make a lithium-ion energy storage element.
The manufacture method of preferably above-mentioned lithium-ion energy storage element, is more contained in the oxygen removal step that the first circle discharge and recharge after injecting ionogen produces.
Preferably, the positive pole framework active substance of step (a) is selected from the group being made up of anatase phase titanium dioxide, carbon-sulfur compound, carbonaceous material and fluorocarbon material.
Preferably, the positive pole framework active substance lithium metal oxide of step (a).
Preferably, step (a) more adds a conductive carbon to make this positive active material, and this conductive carbon is superP carbon black, KS6 graphite or both combinations.
Preferably, the tackiness agent of step (a) is polyvinylidene difluoride (PVDF) or carboxymethyl cellulose.
Preferably, the negative electrode active material of step (c) is selected from the group being made up of greying carbonaceous mesophase spherules, hard carbon, Si alloy and Sn alloy.
Preferably, the ionogen of step (c) is than the LiPF being dissolved with 1M concentration in for the mixing solutions of 1:1 at the mixed volume of ethylene carbonate and diethyl carbonate6, or the sub-acid amides lithium of bis trifluoromethyl sulfonic acid being dissolved with 1M concentration in the mixing solutions for 1:1 is compared at the mixed volume of tetraethyleneglycol dimethyl ether and 1,3-dioxolane.
Preferably, the dispersion agent of step (a) is METHYLPYRROLIDONE.
Specifically, the manufacture method of the lithium-ion energy storage element of the present invention, first by lithium peroxide; Positive pole framework active substance, such as titanium dioxide; And tackiness agent, such as polyvinylidene difluoride (PVDF) (PVDF) is with the mixing of certain weight ratio, and is scattered in METHYLPYRROLIDONE and obtains slurry.Then above-mentioned slurry is poured on aluminium foil, it may also be useful to knife coater is by slurry coating film forming. Coated electrode is inserted in the baking oven of 80 ~ 90 �� of c, removes solvent, be then warming up to 120 ~ 130 �� of c and dry for some time, thus prepare lithium peroxide/titanium dioxide pole piece. In order to increase the conductance of lithium peroxide, conductive carbon can be added, such as superP carbon black, KS6 graphite or both combinations.
Use above-mentioned preparation lithium peroxide/titanium dioxide pole piece, as the greying carbonaceous mesophase spherules (MCMB) of negative pole and porousness barrier film, it it is the ionogen of the LiPF6 being dissolved with 1M concentration in the mixing solutions of 1:1 by the mixed volume ratio at ethylene carbonate (EC) and diethyl carbonate (DEC), inject between above-mentioned lithium peroxide pole piece and negative pole, thus make full battery.
The manufacture method of another kind of lithium-ion energy storage element of the present invention, first by lithium peroxide; Positive pole framework active substance, such as carbon-sulfur compound; And tackiness agent such as carboxymethyl cellulose (CMC) is with the mixing of certain weight ratio, and it is scattered in METHYLPYRROLIDONE and is obtained slurry. Then above-mentioned slurry is poured on aluminium foil, it may also be useful to knife coater is by slurry coating film forming. Coated electrode is inserted in the baking oven of 80 ~ 90 �� of c, removes solvent, be then warming up to 120 ~ 130 �� of c and dry for some time, thus prepare lithium peroxide/carbon-sulfur compound pole piece. In order to increase the conductance of lithium peroxide, conductive carbon can be added, such as superP carbon black, KS6 graphite or both combinations.
Use above-mentioned preparation lithium peroxide/carbon-sulfur compound pole piece, as the hard carbon of negative pole and porousness barrier film, will at tetraethyleneglycol dimethyl ether (TEGDME) and 1, the ionogen of the mixed volume of 3-dioxolane (DOL) acid amides lithium more sub-to the bis trifluoromethyl sulfonic acid being dissolved with 1M concentration in the mixing solutions for 1:1, inject between above-mentioned lithium peroxide pole piece and negative pole, thus make full battery.
Compared to the existing lithium ion battery containing lithium metal oxide, the lithium-ion energy storage element of the present invention, by using the positive active material containing lithium peroxide and positive pole framework active substance, the mode of electrochemical charge is utilized lithium peroxide and/or Lithium Oxide 98min to be decomposed, produce lithium ion, afterwards just can in the full battery of positive pole framework active substance, negative electrode active material embedding repeatedly and embedding go out, high specific capacitance amount can be shown.
Accompanying drawing explanation
Fig. 1 display is according to the unit cell structure of the lithium ion battery of one embodiment of the invention.
Fig. 2 is the 1st cyclic curve figure of the voltage versus capacity of the half-cell discharge and recharge of lithium peroxide of the present invention.
Fig. 3 is the 2nd and 3 cyclic curve figure of the voltage versus capacity of the half-cell discharge and recharge of lithium peroxide of the present invention.
1st cyclic curve figure of the voltage versus capacity of the half-cell discharge and recharge that Fig. 4 is lithium peroxide of the present invention under different conductive carbon ratio.
Fig. 5 is the scanning of the cycle potentials under lithium peroxide and conductive carbon different ratios.
Fig. 6 is the impact of the different current density of display for the voltage versus capacity of lithium peroxide.
Fig. 7 is that lithium peroxide/titanium dioxide is to the preset lithium charging and discharging curve of the half-cell of Li/Li+.
Fig. 8 is the charging and discharging curve of the titanium dioxide after the preset lithium stage.
Fig. 9 is that lithium peroxide/titanium dioxide is to the preset lithium charging and discharging curve of the full battery of greying carbonaceous mesophase spherules (MCMB).
Figure 10 is the charging and discharging curve of the titanium dioxide after the preset lithium stage.
Figure 11 display has the lithium peroxide/titanium dioxide removing oxygen to the preset lithium charging and discharging curve of the full battery of greying carbonaceous mesophase spherules (MCMB).
Figure 12 is the charging and discharging curve of the titanium dioxide after having the preset lithium stage removing oxygen.
Figure 13 shows the charging and discharging curve of the half-cell that lithium peroxide carries out in 2 ~ 4.3V in ether class ionogen relative to lithium metal.
Figure 14 shows the charging and discharging curve of carbon-sulfur compound electrode composition half-cell.
Figure 15 lithium peroxide/carbon-sulfur compound is to Li/Li+The preset lithium charging and discharging curve of half-cell.
Description of reference numerals:
100 unit cell structures;
104 porousness barrier films;
106 positive poles;
105 sticking agents;
108 negative poles;
110 first collection electricity sheets;
112 the 2nd collection electricity sheets;
114 positive active materials;
116 negative electrode active materials.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, so that the technician of this area can better understand the present invention and can be implemented, but illustrated embodiment is not as a limitation of the invention.
Fig. 1 display is according to the unit cell structure of the lithium-ion energy storage element of one embodiment of the invention. The lithium-ion energy storage element of the present embodiment comprises multiple unit cell structure 100, and each unit cell structure 100 comprises porousness barrier film 104 and is interposed between positive pole 106 and negative pole 108. Porousness barrier film 104 is coated with element that tackiness agent 105 increases battery structure 100 connectivity each other. The positive active material 114 that positive pole 106 comprises the first collection electricity sheet 110 and is positioned on the first collection electricity sheet 110, and the negative electrode active material 116 that negative pole 108 comprises the 2nd collection electricity sheet 112 and is positioned on the 2nd collection electricity sheet 112. Positive active material 114 comprises lithium ion supplier and positive pole framework active substance, and wherein lithium ion supplier can be lithium peroxide, positive pole framework active substance such as anatase phase titanium dioxide or carbon-sulfur compound. In carbon-sulfur compound, sulphur carbon ratio example is 5 ~ 7:3 ~ 5. The negative electrode active material 116 of lithium peroxide/titanium dioxide system is carbonaceous material such as greying carbonaceous mesophase spherules (MCMB). The negative electrode active material 116 of lithium peroxide/carbon-sulfur compound system can be carbonaceous material such as hard carbon. The lithium ion supplier of the present invention can be lithium peroxide, but is not limited to lithium peroxide, and such as Lithium Oxide 98min is also applicable. Or, by used in combination to lithium peroxide and Lithium Oxide 98min. In addition, positive pole framework active substance can also select carbonaceous material, and positive and negative electrode like this is all carbonaceous material and forms lithium-ion capacitance. There is the fluorine carbon (CF of high specific discharge capacityx) material is also suitable as the positive pole framework active substance of the present invention. There is the Si alloy of extremely high theoretical electrical capacity or Sn alloy is also suitable as the negative electrode active material 116 of the present invention.
The ionogen being applicable to lithium peroxide/titanium dioxide system can be containing lithium salt such as LiPF6��LiClO4Or LiBF4And organic solvent, such as it is selected from the group group being made up of NSC 11801, diethyl carbonate and diethyl carbonate. The ionogen being applicable to lithium peroxide/carbon-sulfur compound system can be the mixed volume acid amides lithium more sub-to the bis trifluoromethyl sulfonic acid being dissolved with 1M concentration in the mixing solutions for 1:1 of tetraethyleneglycol dimethyl ether (TEGDME) and 1,3-dioxolane (DOL).
The charge and discharge mode of the unit cell structure 100 of the present embodiment, when charging to suitable potential, the positive active material 114 comprising lithium peroxide is decomposed and generates lithium ion and oxygen, in advance using Lithium-ion embeding as in the carbonaceous material of negative pole 108. Upon discharging, the lithium ion being arranged in negative pole 108 diffuses to positive pole 106 via electrolytic solution and embeds positive active material, just can carry out normal discharge and recharge operation afterwards.
First carrying out the electrical discussion of lithium peroxide, the present invention produces lithium ion for utilizing the mode of electrochemical charge to be decomposed by lithium peroxide, afterwards just can in not containing the full battery of lithium ion positive and negative electrode material embedding repeatedly embedding go out. Owing to the conductance of lithium peroxide is not high, conductive carbon can be added to increase the conductance of lithium peroxide.
The present invention provides the manufacture method of a kind of lithium-ion energy storage element, first lithium peroxide and titanium dioxide, conductive carbon (superP carbon black, KS6 graphite or both combinations) and polyvinylidene difluoride (PVDF) (PVDF) are mixed with certain weight ratio, and it is scattered in METHYLPYRROLIDONE (NMP) and obtains slurry. Then above-mentioned slurry is poured on aluminium foil, it may also be useful to knife coater is by slurry coating film forming. Coated electrode is inserted and in the baking oven of 80 �� of c, removes solvent 6 hours, be then warming up to 120 �� of c and dry 4 to 6 hours, thus prepare lithium peroxide/titanium dioxide pole piece.
Use above-mentioned preparation lithium peroxide/titanium dioxide pole piece, as the greying carbonaceous mesophase spherules (MCMB) of negative pole and porousness barrier film, by the mixed volume at ethylene carbonate (EC) and diethyl carbonate (DEC) than the LiPF being dissolved with 1M concentration in for the mixing solutions of 1:16Ionogen, inject between above-mentioned lithium peroxide pole piece and negative pole, thus make full battery. Lithium ion supplier in the positive active material of the present invention can be lithium peroxide, but is not limited to lithium peroxide, and such as Lithium Oxide 98min is also applicable. Or, by used in combination to lithium peroxide and Lithium Oxide 98min. In addition, positive pole framework active substance can also select carbonaceous material, and positive and negative electrode like this is all carbonaceous material and forms lithium-ion capacitance. The fluorocarbon material with high specific discharge capacity is also suitable as the positive pole framework active substance of the present invention. There is the Si alloy of extremely high theoretical electrical capacity or Sn alloy is also suitable as the negative electrode active material 116 of the present invention.
The present invention provides the manufacture method of a kind of lithium-ion energy storage element in addition, first by lithium peroxide and positive pole framework active substance, such as carbon-sulfur compound, conductive carbon (superP carbon black, KS6 graphite or both combinations) and tackiness agent such as carboxymethyl cellulose (CMC) are with the mixing of certain weight ratio, and are scattered in METHYLPYRROLIDONE and obtain slurry. Then above-mentioned slurry is poured on aluminium foil, it may also be useful to knife coater is by slurry coating film forming. Coated electrode is inserted in the baking oven of 80 ~ 90 �� of c, removes solvent, be then warming up to 120 ~ 130 �� of c and dry for some time, thus prepare lithium peroxide/carbon-sulfur compound pole piece. Lithium ion supplier in the positive active material of the present invention can be lithium peroxide, but is not limited to lithium peroxide, and such as Lithium Oxide 98min is also applicable. Or, by used in combination to lithium peroxide and Lithium Oxide 98min. In addition, positive pole framework active substance can also select carbonaceous material, and positive and negative electrode like this is all carbonaceous material and forms lithium-ion capacitance. The fluorocarbon material with high specific discharge capacity is also suitable as the positive pole framework active substance of the present invention. There is the Si alloy of extremely high theoretical electrical capacity or Sn alloy is also suitable as the negative electrode active material 116 of the present invention.
Use above-mentioned preparation lithium peroxide/carbon-sulfur compound pole piece, as the hard carbon of negative pole and porousness barrier film, will at tetraethyleneglycol dimethyl ether (TEGDME) and 1, the ionogen of the mixed volume of 3-dioxolane (DOL) acid amides lithium more sub-to the bis trifluoromethyl sulfonic acid being dissolved with 1M concentration in the mixing solutions for 1:1, inject between above-mentioned lithium peroxide pole piece and negative pole, thus make full battery.
(performance test)
Fig. 2 is the 1st cyclic curve figure of the voltage versus capacity of the half-cell discharge and recharge of lithium peroxide of the present invention. Fig. 3 is the 2nd and 3 cyclic curve figure of the voltage versus capacity of the half-cell discharge and recharge of lithium peroxide of the present invention. Operational condition is as follows: by lithium peroxide, carbon black (superP) and polyvinylidene difluoride (PVDF) (PVDF) respectively with the positive pole prepared by the weight ratio mixing of 10:80:10, with the LiPF being dissolved with 1M concentration in the mixing solutions being 1:1 by the mixed volume ratio at ethylene carbonate (EC) and diethyl carbonate (DEC)6Ionogen, inject porousness barrier film form half-cell. Charging and discharging currents is 100mA/g lithium peroxide, and charging/discharging voltage is 2 ~ 4.6V.
1st cyclic curve figure of the voltage versus capacity of the half-cell discharge and recharge that Fig. 4 is lithium peroxide of the present invention under different conductive carbon ratio. Operational condition is as follows: by lithium peroxide, conductive carbon (superP carbon black: KS6 graphite=1:1) and polyvinylidene difluoride (PVDF) (PVDF) respectively with the positive pole prepared by the weight ratio mixing of X:Y:10, wherein X=80,60,45,30,10, and Y=10,30,45,60,80 are dissolved with the LiPF of 1M concentration with by the mixed volume at ethylene carbonate (EC) and diethyl carbonate (DEC) in for the mixing solutions of 1:16Ionogen, inject porousness barrier film form half-cell. Charging and discharging currents is 10mA/g lithium peroxide, and charging/discharging voltage is 2 ~ 4.8V.
Fig. 5 is the scanning of the cycle potentials under lithium peroxide and conductive carbon different ratios. Operational condition is as follows: scanning speed is 0.4mV/s, lithium peroxide: conductive carbon=X:Y, and wherein X:Y is 10:80 and 30:60. The mixed volume of ethylene carbonate (EC) and diethyl carbonate (DEC) is than the LiPF being dissolved with 1M concentration in the mixing solutions for 1:16The electric current of cycle potentials scanning of ionogen under different voltage, be all 0mA.
Fig. 6 shows the impact of different current density for the voltage versus capacity of lithium peroxide. Operational condition is as follows: by lithium peroxide, conductive carbon (superP carbon black: KS6 graphite=1:1) and polyvinylidene difluoride (PVDF) (PVDF) respectively with the positive pole prepared by the weight ratio mixing of 30:60:10, with the LiPF being dissolved with 1M concentration in the mixing solutions being 1:1 by the mixed volume ratio at ethylene carbonate (EC) and diethyl carbonate (DEC)6Ionogen, inject porousness barrier film form half-cell. Charging and discharging currents is respectively 10mA/g lithium peroxide, 30mA/g lithium peroxide and 50mA/g lithium peroxide, and charging/discharging voltage is 2 ~ 4.8V.
Collocation between lithium peroxide, conductive carbon and tackiness agent is more than described, and current density is on the impact of lithium peroxide discharge and recharge. But, the lithium peroxide of positive terminal belongs to disposable functional material, decomposition of namely can only once charging. Therefore, in discharge process, need to separately there is active substance to receive the lithium ion diffusing to positive pole from negative pole, such as anatase phase titanium dioxide or carbon-sulfur compound.
Initial lithium peroxide charger assembled by several branch is solved lithium ion and diffuses to negative pole and electric discharge lithium ion diffuses to positive pole from negative pole and is called preset lithium charging stage and preset lithium discharge regime by the present invention, follow-up lithium cell titanium dioxide positive pole and negative pole carry out embedding embedding go out be then real work system.
Please refer to Fig. 7 and Fig. 8, Fig. 7 is that lithium peroxide/titanium dioxide is to Li/Li+The preset lithium charging and discharging curve of half-cell, and Fig. 8 is the charging and discharging curve of the titanium dioxide after the preset lithium stage. Charge the stage at preset lithium, first to lithium peroxide with 50mA/gLi2O2Current density charge to 4.8V to Li/Li+, in the discharge regime of preset lithium and follow-up discharge and recharge then to titanium dioxide with 0.1C(1C=335mAh/g) in 1 ~ 3V to Li/Li+Scope carry out discharge and recharge, its half-cell charging and discharging curve is as shown in Figures 7 and 8.Being divided into lithium peroxide charging curve (preset lithium charging stage) and titanium dioxide discharge curve (preset lithium discharge regime) in Fig. 7, the electrical capacity in preset lithium charging stage is 365mA/gLi2O2, and preset lithium discharge regime has 1.8V and 2.7V two discharge platforms, the electrical capacity of 2.7V platform is about 100mAh/gTiO2, it may be the regeneration of redox reaction or lithium peroxide, is considered as side reaction in the present system, and the electrical capacity namely gone out not belongs to titanium dioxide more to be owned. In addition, the electrical capacity obtained after the electrical capacity contributed by side reaction is deducted is about 280mAh/gTiO2��
Then, please refer to Fig. 9 and Figure 10. Fig. 9 be lithium peroxide/titanium dioxide to the preset lithium charging and discharging curve of the full battery of greying carbonaceous mesophase spherules (MCMB), and Figure 10 is the charging and discharging curve of the titanium dioxide after the preset lithium stage. Use negative pole for MCMB in this experiment, its coated powder part by weight is active substance: superP carbon black: KS graphite: tackiness agent is 70:7.5:7.5:15, and then MCMB powder is heavy relatively is coated with in the way of A/C ratio=1 for the lithium peroxide of positive electrode material, conductive carbon, tackiness agent and titanium dioxide. Relative to the electrical capacity of MCMB, calculate lithium peroxide, superP carbon black, KS graphite weight respectively for 0.4219g(22%), and the weight of PVDF and titanium dioxide is respectively 0.1406g(7%) and 0.4858g(27%). Charge the stage at preset lithium, first to lithium peroxide with 50mA/gLi2O2Current density charge to 4.8V to MCMB, in the discharge regime of preset lithium and follow-up discharge and recharge then to titanium dioxide with 0.1C(1C=335mAh/g) in 0 ~ 3V, the scope of MCMB is carried out discharge and recharge, its full battery charging and discharging curve is as shown in FIG. 9 and 10.
By above-mentioned, it is seen that preset lithium ion is truly feasible in the method for positive pole, but process can produce oxygen, and affect the performance of electrochemistry. Therefore, the performance of lithium ion battery is important by the removal of oxygen. At large-scale lithium cell as in the making processes of aluminium foil soft-package battery, activation action can be carried out, namely first circle discharge and recharge is carried out to form the solid state electrolyte interface film of negative pole after injecting ionogen, now ionogen meeting part cracking, reinject after utilizing the mode that vacuumizes to be extracted out by ionogen new ionogen, can carry out normal discharge and recharge. The display of Figure 11 system has the lithium peroxide/titanium dioxide removing oxygen to the preset lithium charging and discharging curve of the full battery of greying carbonaceous mesophase spherules (MCMB), and Figure 12 is the charging and discharging curve of the titanium dioxide after having the preset lithium stage removing oxygen. There is no method from Figure 11 and find out the effect after removing oxygen, but electrical capacity there is no violent decline from Figure 12 follow-up titanium dioxide charge and discharge process, the follow-up discharge and recharge of susceptible of proof is subject to the side reaction impact of preset lithium discharge regime really, and the source of side reaction is then oxygen that preset lithium process of charging lithium peroxide is decomposed out.
In another embodiment, the positive pole framework active substance in positive active material can use carbon-sulfur compound. Lithium peroxide is mixed with carbon-sulfur compound, to replace lithium metal, and utilizes hard carbon to form full battery as negative pole. Owing to the ionogen of lithium-sulfur cell is ether class, the present embodiment uses lithium peroxide: conductive carbon: the weight ratio of tackiness agent=30:60:10, in sub-acid amides lithium (the LiTFSI)/tetraethyleneglycol dimethyl ether (TEGDME) of 1M bis trifluoromethyl sulfonic acid: 1,3-dioxolane (DOL)=1:1(v:v) with 100mA/gLi2O2Current density carry out half-cell test relative to lithium metal in 2 ~ 4.3V, as shown in figure 13.Select charge cutoff voltage to be 4.3V, select 100mA/gLi2O2Carry out about 9 hours of charging. Can find that the lithium peroxide in lithium-sulfur cell electrolyte system decomposes overpotential and is about 4.1V, and the electrical capacity of gained is about 980mAh/gLi2O2��
Figure 14 shows the charging and discharging curve of carbon-sulfur compound electrode composition half-cell. Carbon-sulfur compound electrode is formed half-cell, and wherein sulphur carbon ratio example is 5 ~ 7:3 ~ 5. Afterwards with 0.1C(1C=1672mAh/gs) charge-discharge velocity in 1.5 ~ 3V to Li/Li+Carrying out discharge and recharge, charging and discharging curve is as shown in figure 14.
Figure 15 is that lithium peroxide/carbon-sulfur compound is to Li/Li+The preset lithium charging and discharging curve of half-cell. After acknowledged Lithium Oxide 98min and carbon-sulfur compound other electrochemistry each shows, the mixing of above-mentioned bi-material is made electrode by the present embodiment, using METHYLPYRROLIDONE as dispersion agent when preparing electrode, and with 100mA/gLi2O2Current density preset lithium charge the stage lithium peroxide is charged to 4.3V to Li/Li+, then with 0.1C(1C=1672mAh/gs) carbon-sulfur compound carried out preset lithium electric discharge and follow-up discharge and recharge. The charging and discharging curve of preset lithium charging stage and discharge regime, as shown in figure 15.
The present invention utilizes the mode of electrochemical charge lithium peroxide and/or Lithium Oxide 98min to be decomposed, and produces lithium ion, afterwards just can in the full battery of positive pole framework active substance, negative electrode active material embedding repeatedly and embedding go out, high electrical capacity can be shown. Positive pole framework active substance can be anatase phase titanium dioxide, carbon-sulfur compound, carbonaceous material or fluorocarbon material, but is not limited to this, as long as stability height and to have the material of good electrical capacity all applicable. Even use lithium metal oxide as positive pole framework active substance, it is combined as positive active material with lithium peroxide and/or Lithium Oxide 98min, it is possible to show and use lithium metal oxide as the high electrical capacity of positive active material than simple.
The above embodiment is only the preferred embodiment lifted for absolutely proving the present invention, and protection scope of the present invention is not limited to this. The equivalent replacement that those skilled in the art do on basis of the present invention or conversion, all within protection scope of the present invention. Protection scope of the present invention is as the criterion with claim book.
Claims (14)
1. a lithium-ion energy storage element, it is characterised in that, comprising:
One positive pole, its positive active material comprising one first collection electricity sheet and being positioned on this first collection electricity sheet;
One negative pole, its negative electrode active material comprising one the 2nd collection electricity sheet and being positioned on the 2nd collection electricity sheet, this negative electrode active material is selected from the group being made up of a carbonaceous material, Si alloy and Sn alloy; And
One ionogen, between this positive pole and this negative pole, wherein this positive active material comprises a lithium ion supplier and a positive pole framework active substance, and this lithium ion supplier is lithium peroxide, Lithium Oxide 98min or both mixtures.
2. lithium-ion energy storage element as claimed in claim 1, it is characterised in that, this positive pole framework active substance of this positive active material is selected from the group being made up of anatase phase titanium dioxide, carbon-sulfur compound, carbonaceous material and fluorocarbon material.
3. lithium-ion energy storage element as claimed in claim 2, it is characterised in that, the sulphur carbon ratio example of the carbon-sulfur compound of this positive pole framework active substance is 5 ~ 7:3 ~ 5.
4. lithium-ion energy storage element as claimed in claim 1, it is characterised in that, this positive pole framework active substance is lithium metal oxide.
5. lithium-ion energy storage element as claimed in claim 1, it is characterised in that, this positive active material more comprises a conductive carbon, and this conductive carbon is superP carbon black, KS6 graphite or both combinations.
6. the manufacture method of a lithium-ion energy storage element, it is characterised in that, comprise following step:
A lithium ion supplier, positive pole framework active substance and tackiness agent are mixed by () respectively with certain weight ratio, and be incorporated in and a dispersion agent prepares positive active material, wherein this lithium ion supplier is lithium peroxide, Lithium Oxide 98min or both mixtures;
B this positive active material is applied to an aluminium foil film forming by () after, coated electrode is dried, thus prepares positive pole; And
C () uses this positive pole preparing gained, the negative pole with negative electrode active material and is folded in a porousness barrier film wherein, injected by ionogen between this positive pole and this negative pole, thus make a lithium-ion energy storage element.
7. the manufacture method of lithium-ion energy storage element as claimed in claim 6, it is characterised in that, more it is contained in the oxygen removal step that the first circle discharge and recharge after injecting ionogen produces.
8. the manufacture method of lithium-ion energy storage element as claimed in claim 6, it is characterised in that, the positive pole framework active substance of step (a) is selected from the group being made up of anatase phase titanium dioxide, carbon-sulfur compound, carbonaceous material and fluorocarbon material.
9. the manufacture method of lithium-ion energy storage element as claimed in claim 6, it is characterised in that, the positive pole framework active substance lithium metal oxide of step (a).
10. the manufacture method of lithium-ion energy storage element as claimed in claim 6, it is characterised in that, step (a) more adds a conductive carbon to make this positive active material, and this conductive carbon is superP carbon black, KS6 graphite or both combinations.
The manufacture method of 11. lithium-ion energy storage elements as claimed in claim 6, it is characterised in that, the tackiness agent of step (a) is polyvinylidene difluoride (PVDF) or carboxymethyl cellulose.
The manufacture method of 12. lithium-ion energy storage elements as claimed in claim 6, it is characterised in that, the negative electrode active material of step (c) is selected from the group being made up of greying carbonaceous mesophase spherules, hard carbon, Si alloy and Sn alloy.
The manufacture method of 13. lithium-ion energy storage elements as claimed in claim 6, it is characterised in that, the ionogen of step (c) is than the LiPF being dissolved with 1M concentration in for the mixing solutions of 1:1 at the mixed volume of ethylene carbonate and diethyl carbonate6, or the sub-acid amides lithium of bis trifluoromethyl sulfonic acid being dissolved with 1M concentration in the mixing solutions for 1:1 is compared at the mixed volume of tetraethyleneglycol dimethyl ether and 1,3-dioxolane.
The manufacture method of 14. lithium-ion energy storage elements as claimed in claim 6, it is characterised in that, the dispersion agent of step (a) is METHYLPYRROLIDONE.
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