CN103367696A - Anode plate, preparation method thereof and lithium ion battery - Google Patents
Anode plate, preparation method thereof and lithium ion battery Download PDFInfo
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- CN103367696A CN103367696A CN2012100882775A CN201210088277A CN103367696A CN 103367696 A CN103367696 A CN 103367696A CN 2012100882775 A CN2012100882775 A CN 2012100882775A CN 201210088277 A CN201210088277 A CN 201210088277A CN 103367696 A CN103367696 A CN 103367696A
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Abstract
The invention belongs to the field of batteries, and discloses an anode plate, a preparation method thereof and a lithium ion battery. The anode plate comprises a current collector and an anode active material which is coated on the current collector and contains graphene derivant as a component. The anode plate prepared by the invention has the beneficial effects that: (1) as the graphene derivant does not contain lithium, a lithium storage operation with complex technology does not need to be carried out on the graphene derivant, so that the operation technology is simplified, and the manufacturing cost is reduced; (2) the anode plate and a lithium metal cathode form a battery, when the battery charges and discharges, a dendritic crystal is difficult to generate, so that the short circuit problem in the interior of the battery can be avoided; (3) the anode plate and a cathode which does not contain lithium metal form the battery, when the battery charges and discharges, the dendritic crystal is difficult to generate, so that the short circuit problem in the interior of the battery can be avoided.
Description
Technical field
The present invention relates to field of batteries, relate in particular to a kind of positive plate and preparation method thereof.The invention still further relates to a kind of this positive plate that uses as the lithium ion battery of electrode.
Background technology
The positive electrode of existing lithium ion battery mainly adopts inorganic metal compound, and it mainly comprises the system of LiFePO4, LiMn2O4, cobalt acid lithium, lithium nickelate and mixing; The inorganic metal compound class is during as positive electrode, and its complicated process of preparation, cost are high.
In recent years, also developed some organic compounds as positive electrode, but because low, the thermal stability of these positive electrode conductivity and bad mechanical property, and battery cycle life is low, and therefore, the positive electrode discomfort of these organic compounds is fit to do electrode material.
When lithium ion battery adopted organic compound as positive electrode, negative pole generally adopted lithium metal, and lithium metal is in charge and discharge process, and the lithium surface is dissolving and precipitation constantly, and produces easily dendrite, causes internal short-circuit of battery.
Summary of the invention
One of problem to be solved by this invention is to provide a kind of low cost of manufacture, technique is simple and be difficult for causing the preparation method of the positive plate of internal short-circuit of battery.
Technical scheme of the present invention is as follows:
A kind of preparation method of positive plate comprises the steps:
S1, preparation positive electrode active materials: the graphite oxide powder is dissolved in the DMF solution, and ultrasonic agitation obtains the suspension of 1g/L; Under vigorous stirring, add subsequently the anhydrous acetonitrile that contains 5-amino-Isosorbide-5-Nitrae naphthoquinones; Then 80~100 ℃ of reflow treatment 12~24h under inert gas shielding obtain the graphite oxide derivative; Last again with graphite oxide derivative powder and reducing agent backflow 12~24h under 80~100 ℃ of gained, obtain the positive electrode active materials that component is the Graphene derivative; Wherein, in the anhydrous acetonitrile, the mass concentration of 5-amino-Isosorbide-5-Nitrae naphthoquinones is 1g/L;
S2, preparation positive plate: positive electrode active materials and PVDF binding agent that step S1 is made are dissolved in the nmp solution, make gluey positive electrode, subsequently gluey positive electrode is coated on the surface of collector, leaves standstill and carry out the drying processing after 24~48 hours, make positive plate.
The preparation method of described positive plate, among the step S1, the mass ratio of graphite oxide and 5-amino-Isosorbide-5-Nitrae naphthoquinones is 3: 5.
The preparation method of described positive plate, among the step S1, described reducing agent is selected from hydrazine hydrate, sodium borohydride, ethylenediamine or phenylhydrazine.
The preparation method of described positive plate, among the step S1, the mol ratio of described graphite oxide derivative powder and reducing agent is 1: 1.
The preparation method of described positive plate among the step S2, in gluey positive electrode configuration, also needs to add conductive agent; Described conductive agent is selected from acetylene black; The mass ratio of described positive electrode active materials, conductive agent, binding agent is 90: 5: 5.
The preparation method of described positive plate, among the step S2, described collector is selected from aluminium foil.
Two of problem to be solved by this invention is to provide a kind of positive plate, and this positive plate adopts said method to make.
Three of problem to be solved by this invention is to provide a kind of lithium ion battery, and this lithium ion battery comprises the above-mentioned positive plate that makes.
The positive plate that the present invention makes has following beneficial effect: (1) does not need the Graphene derivative is carried out the storage lithium operation of complex process because Graphene derivative itself does not contain lithium, has simplified operating procedure, reduces manufacturing cost; When (2) this positive plate and lithium anode form battery, when it discharges and recharges, be difficult for producing dendrite, also just avoided the internal short-circuit of battery problem.
Description of drawings
Fig. 1 is preparation technology's flow chart of the positive plate of preferred embodiment;
Fig. 2 is the structural representation of the positive plate of preferred embodiment;
Fig. 3 is the structural representation of the lithium ion battery of preferred embodiment.
Embodiment
The preparation method of a kind of positive plate of present embodiment as shown in Figure 1, comprises the steps:
S1, preparation positive electrode active materials: the graphite oxide powder is dissolved in the DMF solution, and ultrasonic agitation obtains the suspension of 1g/L; Under vigorous stirring, add subsequently the anhydrous acetonitrile that contains 5-amino-Isosorbide-5-Nitrae naphthoquinones; Then inert gas (such as, nitrogen, argon gas, the perhaps mist of nitrogen and argon gas) 80~100 ℃ of reflow treatment 12~24h of protection, obtain the graphite oxide derivative; Last again with graphite oxide derivative powder and reducing agent backflow 12~24h under 80~100 ℃ of gained, obtain the positive electrode active materials that component is the Graphene derivative; Wherein, in the anhydrous acetonitrile, the mass concentration of 5-amino-Isosorbide-5-Nitrae naphthoquinones is 1g/L;
S2, preparation positive plate: positive electrode active materials and PVDF binding agent that step S1 is made are dissolved in the nmp solution, make gluey positive electrode, subsequently gluey positive electrode is coated on the surface of collector, leaves standstill and carry out the drying processing after 24~48 hours, make positive plate.
The preparation method of described positive plate, among the step S1:
Preferably, the mass ratio of graphite oxide and 5-amino-Isosorbide-5-Nitrae naphthoquinones is 3: 5;
Preferably, described reducing agent is selected from hydrazine hydrate, sodium borohydride, ethylenediamine, phenylhydrazine or to biphenol;
Preferably, the mol ratio of described graphite oxide derivative powder and reducing agent is 1: 1.
Preferably, in gluey positive electrode configuration, also need to add conductive agent; Described conductive agent is selected from acetylene black (please inventor perfect); The mass ratio of described positive electrode active materials, conductive agent, binding agent is 90: 5: 5;
Preferably, described collector is selected from aluminium foil.
A kind of positive plate, as shown in Figure 2, this positive plate 1 and comprise aluminum foil current collector 11 and be coated in positive electrode 12 on the aluminum foil current collector 11 that described positive electrode comprises positive electrode active materials and the binding agent take the Graphene derivative as component.
In order to increase the conductivity of positive plate, also comprise conductive agent acetylene black in the preferred positive electrode, and the mass ratio of described positive electrode active materials, conductive agent, binding agent is 90: 5: 5.
The positive plate that present embodiment makes has following beneficial effect: (1) does not need the Graphene derivative is carried out the storage lithium operation of complex process because Graphene derivative itself does not contain lithium, has simplified operating procedure, reduces manufacturing cost; When (2) this positive plate and lithium anode form battery, when it discharges and recharges, be difficult for producing dendrite, also just avoided the internal short-circuit of battery problem; When (3) negative pole of this positive plate and containing metal lithium forms battery, when it discharges and recharges, be difficult for producing dendrite, also just avoided the internal short-circuit of battery problem.
A kind of lithium ion battery, as shown in Figure 3, this lithium ion battery comprises the above-mentioned positive plate that makes 1, barrier film 3, negative plate 2, electrolyte 4 and aluminum plastic film 5; Wherein, positive plate 1, barrier film 3, negative plate 2 der group pack with aluminum plastic film 5 after dressing up battery core, and this moment, aluminum plastic film 5 also just consisted of the shell of battery; Then (component is LiPF toward aluminum plastic film 5 interior filling electrolyte 4
6/ PC+DMC, concentration is 1mol/L), make lithium ion battery; Wherein, negative plate 2 comprises Copper Foil collector 21, lithium sheet 22 and is coated in negative material 23 on the Copper Foil collector, this negative material comprise negative active core-shell material (as, graphite, Graphene, silicon carbon material, hard charcoal etc.), conductive agent (as, acetylene black) and binding agent (as, PVDF).
The lithium ion battery of present embodiment is owing to add in advance lithium sheet (can be according to required battery capacity, suitable adding lithium sheet quantity) in the negative plate; Like this, first during discharge process, the lithium ion in the electrolyte is just transferred on the positive plate at lithium ion battery, makes on the positive plate storage or is enriched with lithium ion; The lithium sheet also constantly has lithium atom to change into lithium ion under electrochemical action simultaneously, adds to electrolyte; Therefore, this lithium ion battery just can not consume the lithium ion in the electrolyte in charge and discharge process, and the capacity of material also can fully play simultaneously, and the transformation efficiency of battery also just is improved.
The below is described in further detail preferred embodiment of the present invention.
Following embodiment 1~4 is the preparation of positive plate
1, the preparation of positive electrode active materials: the graphite oxide of 30mL 1g/L joined fill DMF solution there-necked flask, ultrasonic agitation 1h fully dissolves graphite oxide, obtains suspension; Add subsequently the anhydrous acetonitrile of the 5-amino of 50mL 1g/L-Isosorbide-5-Nitrae naphthoquinones under vigorous stirring, the lower 80 ℃ of backflow 24h of nitrogen protection obtain the graphite oxide derivative; Last again with the graphite oxide derivative powder of 29.3g gained and 5g hydrazine hydrate at 80 ℃ of lower backflow 24h, obtain the positive electrode active materials that component is the Graphene derivative;
2, the preparation of positive plate: positive electrode active materials, conductive agent acetylene black and the PVDF binding agent that step 1 is made is dissolved in the nmp solution with 90: 5: 5 mass ratio, make gluey positive electrode, subsequently gluey positive electrode is coated on the surface of aluminum foil current collector, leave standstill and carry out the drying processing after 24 hours, make positive plate.
Embodiment 2
1, the preparation of positive electrode active materials: the graphite oxide of 60mL 1g/L joined fill DMF solution there-necked flask, ultrasonic agitation 1h fully dissolves graphite oxide, obtains suspension; Add subsequently the anhydrous acetonitrile of the 5-amino of 100mL 1g/L-Isosorbide-5-Nitrae naphthoquinones under vigorous stirring, the lower 100 ℃ of backflow 12h of argon shield obtain the graphite oxide derivative; Last again with the graphite oxide derivative powder of 25.4g gained and 3.3g sodium borohydride at 100 ℃ of lower backflow 12h, obtain the positive electrode active materials that component is the Graphene derivative;
2, the preparation of positive plate: positive electrode active materials, conductive agent acetylene black and the PVDF binding agent that step 1 is made is dissolved in the nmp solution with 90: 5: 5 mass ratio, make gluey positive electrode, subsequently gluey positive electrode is coated on the surface of aluminum foil current collector, leave standstill and carry out the drying processing after 48 hours, make positive plate.
1, the preparation of positive electrode active materials: the graphite oxide of 60mL 1g/L joined fill DMF solution there-necked flask, ultrasonic agitation 1h fully dissolves graphite oxide, obtains suspension; Add subsequently the anhydrous acetonitrile of the 5-amino of 100mL 1g/L-Isosorbide-5-Nitrae naphthoquinones under vigorous stirring, argon gas and nitrogen mixture are protected lower 90 ℃ of backflow 18h, obtain the graphite oxide derivative; Last again with the graphite oxide derivative powder of 27.3g gained and 5.6g ethylenediamine at 90 ℃ of lower backflow 18h, obtain the positive electrode active materials that component is the Graphene derivative;
2, the preparation of positive plate: positive electrode active materials, conductive agent acetylene black and the PVDF binding agent that step 1 is made is dissolved in the nmp solution with 90: 5: 5 mass ratio, subsequently gluey positive electrode is coated on the surface of aluminum foil current collector, leave standstill and carry out the drying processing after 36 hours, make positive plate.
1, the preparation of positive electrode active materials: the graphite oxide of 60mL 1g/L joined fill DMF solution there-necked flask, ultrasonic agitation 1h fully dissolves graphite oxide, obtains suspension; Add subsequently the anhydrous acetonitrile of the 5-amino of 100mL 1g/L-Isosorbide-5-Nitrae naphthoquinones under vigorous stirring, argon gas and nitrogen mixture are protected lower 85 ℃ of backflow 20h, obtain the graphite oxide derivative; Last again with the graphite oxide derivative powder of 28.1g gained and 10.4g phenylhydrazine at 85 ℃ of lower backflow 20h, obtain the positive electrode active materials that component is the Graphene derivative;
2, the preparation of positive plate: positive electrode active materials, conductive agent acetylene black and the PVDF binding agent that step 1 is made is dissolved in the nmp solution with 90: 5: 5 mass ratio, subsequently gluey positive electrode is coated on the surface of aluminum foil current collector, leave standstill and carry out the drying processing after 42 hours, make positive plate.
Following embodiment 5~8 is the preparation of lithium ion battery, and before the lithium ion battery use, with discharging and recharging instrument it is discharged first.
Embodiment 5
1, the preparation of negative plate: adopt conventional method, the negative active core-shell material coated with graphite (is asked the inventor contrasts needs perfect negative plate in the embodiment preparation method, determined the related content in the present embodiment) on copper current collector;
2, positive plate adopts the positive plate that makes among the embodiment 1;
3, the assembling of battery: at first, with positive plate, barrier film, negative plate, carry out the consistent size of cutting according to required specification; Then, in glove box, the positive plate, barrier film, the negative plate that cut out are dressed up battery core according to the der group of positive pole, barrier film, negative pole, use again aluminum plastic film sealed package battery core; At last, implantation concentration is the LiPF of 1mol/L in the aluminum plastic film
6/ PC+DMC electrolyte obtains lithium ion battery.
Embodiment 6
1, the preparation of negative plate: adopt conventional method, the negative active core-shell material coated with graphite (is asked the inventor contrasts needs perfect negative plate in the embodiment preparation method, determined the related content in the present embodiment) on copper current collector;
2, positive plate adopts the positive plate that makes among the embodiment 2;
3, the assembling of battery: at first, with positive plate, barrier film, negative plate, carry out the consistent size of cutting according to required specification; Then, in glove box, the positive plate, barrier film, the negative plate that cut out are dressed up battery core according to the der group of positive pole, barrier film, negative pole, use again aluminum plastic film sealed package battery core; At last, implantation concentration is the LiPF of 1mol/L in the aluminum plastic film
6/ PC+DMC electrolyte obtains lithium ion battery.
Embodiment 7
1, the preparation of negative plate: adopt conventional method, the negative active core-shell material coated with graphite (is asked the inventor contrasts needs perfect negative plate in the embodiment preparation method, determined the related content in the present embodiment) on copper current collector;
2, positive plate adopts the positive plate that makes among the embodiment 3;
3, the assembling of battery: at first, with positive plate, barrier film, negative plate, carry out the consistent size of cutting according to required specification; Then, in glove box, the positive plate, barrier film, the negative plate that cut out are dressed up battery core according to the der group of positive pole, barrier film, negative pole, use again aluminum plastic film sealed package battery core; At last, implantation concentration is the LiPF of 1mol/L in the aluminum plastic film
6/ PC+DMC electrolyte obtains lithium ion battery.
Embodiment 8
1, the preparation of negative plate: adopt conventional method, the negative active core-shell material coated with graphite (is asked the inventor contrasts needs perfect negative plate in the embodiment preparation method, determined the related content in the present embodiment) on copper current collector;
2, positive plate adopts the positive plate that makes among the embodiment 4;
3, the assembling of battery: at first, with positive plate, barrier film, negative plate, carry out the consistent size of cutting according to required specification; Then, in glove box, the positive plate, barrier film, the negative plate that cut out are dressed up battery core according to the der group of positive pole, barrier film, negative pole, use again aluminum plastic film sealed package battery core; At last, implantation concentration is the LiPF of 1mol/L in the aluminum plastic film
6/ PC+DMC electrolyte obtains lithium ion battery.
Should be understood that above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. the preparation method of a positive plate is characterized in that, comprises the steps:
S1, preparation positive electrode active materials: the graphite oxide powder is dissolved in the DMF solution, and ultrasonic agitation obtains the suspension of 1g/L; Under vigorous stirring, add subsequently the anhydrous acetonitrile that contains 5-amino-Isosorbide-5-Nitrae naphthoquinones; Then 80~100 ℃ of reflow treatment 12~24h under inert gas shielding obtain the graphite oxide derivative; Last again with graphite oxide derivative powder and reducing agent backflow 12~24h under 80~100 ℃ of gained, obtain the positive electrode active materials that component is the Graphene derivative; Wherein, in the anhydrous acetonitrile, the mass concentration of 5-amino-Isosorbide-5-Nitrae naphthoquinones is 1g/L;
S2, preparation positive plate: positive electrode active materials and PVDF binding agent that step S1 is made are dissolved in the nmp solution, make gluey positive electrode; Subsequently gluey positive electrode is coated on the surface of collector, leaves standstill and carry out the drying processing after 24~48 hours, make positive plate.
2. the preparation method of positive plate according to claim 1 is characterized in that, among the step S1, the mass ratio of graphite oxide and 5-amino-Isosorbide-5-Nitrae naphthoquinones is 3: 5.
3. the preparation method of positive plate according to claim 1 is characterized in that, among the step S1, described reducing agent is selected from hydrazine hydrate, sodium borohydride, ethylenediamine or phenylhydrazine.
4. according to claim 1 or the preparation method of 3 described positive plates, it is characterized in that among the step S1, the mol ratio of described graphite oxide derivative powder and reducing agent is 1: 1.
5. the preparation method of positive plate according to claim 1 is characterized in that, among the step S2, in gluey positive electrode configuration, also needs to add conductive agent; Described conductive agent is selected from acetylene black; The mass ratio of described positive electrode active materials, conductive agent, binding agent is 90: 5: 5.
6. the preparation method of positive plate according to claim 1 is characterized in that, among the step S2, described collector is selected from aluminium foil.
7. a positive plate is characterized in that, this positive plate adopts as claimed in claim 1 that method makes.
8. a lithium ion battery is characterized in that, comprises positive plate as claimed in claim 9.
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Cited By (2)
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CN104183824A (en) * | 2014-09-09 | 2014-12-03 | 南京中储新能源有限公司 | Graphene/quinones composite material, preparation method and secondary cell |
CN104752727A (en) * | 2013-12-31 | 2015-07-01 | 华为技术有限公司 | Quinone compound-graphene composite material and preparation method thereof as well as flexible lithium secondary battery |
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CN104752727A (en) * | 2013-12-31 | 2015-07-01 | 华为技术有限公司 | Quinone compound-graphene composite material and preparation method thereof as well as flexible lithium secondary battery |
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Application publication date: 20131023 |