CN104766947A - Preliminary metal metallization method and its application in battery material - Google Patents
Preliminary metal metallization method and its application in battery material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a preliminary metal metallization method and its application in a battery material. The method comprises the following steps: dissolving a polycyclic aromatic compound with the concentration of 0.005-10mol/L in an organic solvent in inert atmosphere at room temperature to form a precursor solution; adding an alkali metal into the precursor solution; and standing for 0.5-48h to dissolve the alkali metal in the precursor solution in order to form a black or dark green or pale yellow alkali metallization solution, wherein the content of the alkali metal in the alkali metallization solution is 0.005-150g/L.
Description
Technical field
The present invention relates to materialogy field, particularly relate to a kind of method of alkali metal in advance and the application in battery material thereof.
Background technology
Contemporary society's energy crisis and environmental problem highlight day by day, and the storage of the novel clean energy and energy has become the focus of people's research.In this context, lithium ion battery is because of its high-energy-density, high power density, the feature such as long-life and environmental friendliness, substantially, captured the market of portable consumer electronics product, and had broad application prospects in electric automobile, the extensive field such as energy storage device, distributing portable power source.
The operation principle of lithium ion battery is based on the repeatedly deintercalation of lithium ion in positive and negative pole material, and it is since commercialization, mostly adopts positive pole to provide the mode in lithium source.But along with the growth of people's demand, development high energy density cells becomes the task of top priority, but LiCoO most widely used at present
2capacity lower (140mAh/g), and not overcharging resisting, and by contrast, non-lithium source positive pole, such as V
2o
5, Cr
3o
8etc. can form a series of lithium intercalation compound, capacity can reach 250mAh/g, has more excellent performance, but because itself is containing lithium, uses seldom in current common lithium-ion battery system.On the other hand, people have developed a series of high-capacity cathode material successively, such as hard carbon, tin, silicon, transition metal oxide etc., but these materials have first all inefficient problems.First all inefficient main causes are that material, in all cyclic processes of head, irreversible lithiation occurs, wherein modal is that material surface forms passivating film, the passivating film formed can stop passing through of solvent molecule effectively, but lithium ion freely can pass through this passivation layer, there is the feature of solid electrolyte, therefore this layer of passivating film is called as " solid electrolyte interface film " (solid electrolyte interface, SEI), this layer of SEI film can consume part lithium source, causes this part lithium can not participate in follow-up embedding lithium and de-lithium.And in full battery, first all efficiency directly determines the energy density of battery.And if the lithium of the mode compensated in advance loss of reaction of prelithiation can be carried out by anticathode, then greatly can improve the head week efficiency and energy density thereof of battery.
Lithiumation belongs to the one of alkali metalization reaction, and in chemical reaction, alkali metal is the class reaction be incorporated into by alkali metal in reactant.The more lithiumation mode of current use is adopt lithium metal, but directly adopts lithium metal must carry out under anhydrous dry environment, and require higher, carrying out stabilization processes to metallic lithium powder then needs more complicated technique just can reach desirable effect.The another kind of means of prelithiation use to react containing the chemical reagent of lithium and active material.More reagent is used to have the cyclohexane solution of butyl lithium and the anhydrous acetonitrile of LiI.But butyl lithium reproducibility is too high, contacting with oxygen can directly blast, and require strict to the oxygen content in operating environment, acetonitrile solution has severe toxicity simultaneously, to human body and environmental hazard quite large.In addition, sodium and the potassiumization document of being correlated with at present and report all considerably less.
Accompanying drawing explanation
Below by drawings and Examples, the technical scheme of the embodiment of the present invention is described in further detail.
The flow chart of the method for the alkali metal in advance that Fig. 1 provides for the embodiment of the present invention;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Fig. 2 provides for the embodiment of the present invention 5 after the method process of alkali metal in advance;
The cycle performance of the lithium ion of the lithium ion battery negative electrode that Fig. 3 provides for the embodiment of the present invention 5 after the method process of alkali metal in advance and coulombic efficiency;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Fig. 4 provides for the embodiment of the present invention 6 after the method process of alkali metal in advance;
The cycle performance of the lithium ion of the lithium ion battery negative electrode that Fig. 5 provides for the embodiment of the present invention 6 after the method process of alkali metal in advance and coulombic efficiency;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Fig. 6 provides for the embodiment of the present invention 7 after the method process of alkali metal in advance;
The cycle performance of the lithium ion of the lithium ion battery negative electrode that Fig. 7 provides for the embodiment of the present invention 7 after the method process of alkali metal in advance and coulombic efficiency;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Fig. 8 provides for the embodiment of the present invention 8 after the method process of alkali metal in advance;
The cycle performance of the lithium ion of the lithium ion battery negative electrode that Fig. 9 provides for the embodiment of the present invention 8 after the method process of alkali metal in advance and coulombic efficiency;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Figure 10 provides for the embodiment of the present invention 9 after the method process of alkali metal in advance;
The cycle performance of the lithium ion of the lithium ion battery negative electrode that Figure 11 provides for the embodiment of the present invention 9 after the method process of alkali metal in advance and coulombic efficiency;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Figure 12 provides for the embodiment of the present invention 10 after the method process of alkali metal in advance;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Figure 13 provides for the embodiment of the present invention 11 after the method process of alkali metal in advance;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Figure 14 provides for the embodiment of the present invention 12 after the method process of alkali metal in advance;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Figure 15 provides for the embodiment of the present invention 13 after the method process of alkali metal in advance;
The cycle performance of the lithium ion of the lithium ion battery negative electrode that Figure 16 provides for the embodiment of the present invention 13 after the method process of alkali metal in advance and coulombic efficiency;
The charging and discharging curve of the lithium ion battery of the lithium ion battery negative electrode that Figure 17 provides for the embodiment of the present invention 14 after the method process of alkali metal in advance;
The cycle performance of the lithium ion of the lithium ion battery negative electrode that Figure 18 provides for the embodiment of the present invention 14 after the method process of alkali metal in advance and coulombic efficiency;
The charging and discharging curve of lithium ion battery in the prior art that Figure 19 provides for comparative example 1 of the present invention;
The cycle performance of lithium ion battery and coulombic efficiency in the prior art that Figure 20 provides for comparative example 1 of the present invention;
The charging and discharging curve of lithium ion battery in the prior art that Figure 21 provides for comparative example 2 of the present invention;
The cycle performance of lithium ion battery and coulombic efficiency in the prior art that Figure 22 provides for comparative example 2 of the present invention;
The charging and discharging curve of lithium ion battery in the prior art that Figure 23 provides for comparative example 3 of the present invention;
The cycle performance of lithium ion battery and coulombic efficiency in the prior art that Figure 24 provides for comparative example 3 of the present invention.
Summary of the invention
Embodiments provide a kind of method of alkali metal in advance and the application in battery material thereof.The method of the alkali metal in advance based on chemical method provided by the invention, be easy to operation, prepared alkali metal solution is easy to preserve, cheap, can be used in the preparation of cell positive material and the pre-alkali metal process of negative pole piece of battery, alkali metal ability is strong, and environmental protection, has the prospect of extensive use.
First aspect, embodiments provides a kind of method of alkali metal in advance, comprising:
Under room temperature, in an inert atmosphere, be that the polycyclc aromatic compound of 0.005mol/L ~ 10mol/L is dissolved in organic solvent and forms precursor aqueous solution by concentration;
Alkali metal is added in described precursor aqueous solution;
Leave standstill 0.5 ~ 48 hour, described dissolved alkali metal, in precursor aqueous solution, forms the blackish green or lurid alkali metal solution of black; Wherein, in described alkali metal solution, alkali-metal content is 0.005g/L ~ 150g/L.
Preferably, described alkali metal be in Powdered, sheet, bar-shaped or band shape any one or multiple.
Preferably, described alkali metal comprises one or more in lithium, sodium, potassium, rubidium, caesium, francium.
Preferably, described polycyclc aromatic compound is specially one or more in naphthalene, biphenyl, terphenyl, quaterphenyl, anthracene, phenanthrene and derivative thereof.
Preferably, described organic solvent is specially dimethyl ether, diethyl ether, glycol dimethyl ether, butyl cellosolve, dibutyl ethylene glycol ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, one or more in propylene glycol diethyl ether.
Preferably, described alkali-metal content is 0.5g/L ~ 60g/L.
In second aspect, alkali metal solution prepared by a kind of method described in above-mentioned first aspect that embodiments provides, for the preparation method of cell positive material, comprising:
Described alkali metal solution is mixed with anode raw material, after standing, cleaning and filtering, vacuumize, prepares cell positive material;
Described anode raw material comprise: a kind of or arbitrary proportion of vanadic oxide, chromium three oxygen eight, ferric phosphate, cobalt oxide, LiMn2O4, nickel oxide, manganous oxide several.
In the third aspect, alkali metal solution prepared by a kind of method described in above-mentioned first aspect that embodiments provides, for the pretreated method of negative pole piece of battery, comprising:
In an inert atmosphere or under vacuum environment, negative pole piece of battery being contacted with described alkali metal solution, through leaving standstill, cleaning, after vacuumize, preparing pretreated negative pole piece of battery.
Preferably, described contact is specially: solution left standstill contacts; Wherein, the time of contact of described alkali metal solution and described negative pole piece of battery is 5 seconds ~ 30 minutes.
Preferably, described contact is specially: shower nozzle spraying contact; Wherein, the spray speed of shower nozzle spraying is 0.05ml/s ~ 50ml/s.
Preferably, described contact is specially: coated with Contact; Wherein, described alkali metal solution coat amount is 0.05ml/cm
2~ 10ml/cm
2.
Preferably, in the process that described negative pole piece of battery contacts with described alkali metal solution, heat treated is carried out to described negative pole piece of battery and described alkali metal solution; Wherein, the temperature of described heat treated is 40 DEG C ~ 100 DEG C.
Preferably, described negative pole piece of battery is prepared by negative electrode active material;
Described negative electrode active material comprises: hard carbon, carbonaceous mesophase spherules (MCMB), Delanium, native graphite, lithium titanate, nano-silicon, micron silicon, tin, antimony, germanium, transition metal oxide, and above material surface is coated with hard carbon, carbonaceous mesophase spherules MCMB, Delanium, native graphite, titanium oxide, lithium titanate, sodium titanate, the Na of carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer
0.66li
0.22ti
0.78o
2, nano-silicon, micron silicon, tin, antimony, germanium, a kind of or arbitrary proportion in transition metal oxide several.
The method of a kind of alkali metal in advance that the embodiment of the present invention provides, be easy to realize, prepared alkali metal solution is easy to preserve, cheap, can be used in the preparation of cell positive material and the pre-alkali metal process of negative pole piece of battery, alkali metal ability is strong, and environmental protection, has the prospect of extensive use.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not intended to limit the scope of the invention.
Embodiment 1
The embodiment of the present invention 1 provides a kind of method of alkali metal in advance, also can be called the preparation method of alkali metal solution, described alkali metal in advance comprises lithiumation, in advance sodium, in advance potassium, in advance rubidium, in advance caesium in advance and one or more in advance in francium.
Concrete, as shown in Figure 1, described method comprises:
Concentration under room temperature, in an inert atmosphere, is that the polycyclc aromatic compound of 0.005mol/L ~ 10mol/L is dissolved in organic solvent and forms precursor aqueous solution by step 101;
Concrete further, described polycyclc aromatic compound be specially in naphthalene, biphenyl, terphenyl, quaterphenyl, anthracene, phenanthrene and derivative thereof one or more; Described organic solvent is specially dimethyl ether, diethyl ether, glycol dimethyl ether, butyl cellosolve, dibutyl ethylene glycol ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, one or more in propylene glycol diethyl ether.
Step 102, adds alkali metal in described precursor aqueous solution;
Concrete further, alkali metal comprise in lithium, sodium, potassium, rubidium, caesium, francium one or more, its concrete form be in Powdered, sheet, bar-shaped or band shape any one or multiple.
Step 103, leaves standstill 0.5 ~ 48 hour, and described dissolved alkali metal, in precursor aqueous solution, forms the blackish green or lurid alkali metal solution of black; Wherein, in described alkali metal solution, alkali-metal content is 0.005g/L ~ 150g/L.
In a preferred example, alkali-metal content is 0.5g/L ~ 60g/L.
The method of the alkali metal in advance that the embodiment of the present invention 1 provides realizes based on chemical method, and be easy to operation, preparation cost is cheap, and prepared alkali metal solution is easy to preserve, and alkali metal ability is strong.
Embodiment 2
The embodiment of the present invention 2 in order to alkali metal solution prepared by the method for alkali metal in advance according to above-described embodiment 1 to be described, for the synthesis of the method preparing cell positive material.
Concrete, described method comprises:
Described alkali metal solution is mixed with anode raw material, after standing, cleaning and filtering, vacuumize, prepares cell positive material;
Concrete, described positive electrode comprises the several of a kind of or arbitrary proportion of vanadic oxide, chromium three oxygen eight, ferric phosphate, cobalt oxide, LiMn2O4, nickel oxide, manganous oxide.
The process of alkali metal in advance of concrete positive electrode can be as follows.
Get positive electrode and alkali metal solution, be positioned in container, the alkali metal mol ratio in positive electrode and alkali metal solution is 1:1.Leave standstill 24 ~ 48 hours, mixed solution becomes clarification.Positive electrode is filtered, and spent glycol dimethyl ether repeatedly washes away biphenyl clearly repeatedly, the cell positive material of the method synthesis preparation with alkali metal in advance of the present invention after vacuumize, can be obtained.
Embodiment 3
The embodiment of the present invention 3, in order to alkali metal solution prepared by the method for the alkali metal in advance according to above-described embodiment 1 to be described, carries out the method for alkali metal in advance for the negative material in battery electrode material.
Described negative material comprises hard carbon, carbonaceous mesophase spherules (MCMB), Delanium, native graphite, lithium titanate, nano-silicon, micron silicon, tin, antimony, germanium, transition metal oxide, and above material surface is coated with hard carbon, carbonaceous mesophase spherules (MCMB), Delanium, native graphite, titanium oxide, lithium titanate, sodium titanate, the Na of carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer
0.66li
0.22ti
0.78o
2, nano-silicon, micron silicon, tin, antimony, germanium, a kind of or arbitrary proportion in transition metal oxide several.
Concrete preparation process is with embodiment 2, and the organic solvent that the negative material being alkali metal in advance with embodiment 2 difference cleans is one or more in benzene, toluene or 1-METHYLPYRROLIDONE.
Embodiment 4
Embodiment 4, in order to alkali metal solution prepared by the method for the alkali metal in advance according to above-described embodiment 1 to be described, carries out the method for alkali metal in advance for battery pole piece.
Described battery pole piece is that one or more negative electrode active materials are prepared.Concrete, the hard carbon that negative electrode active material is hard carbon, carbonaceous mesophase spherules (MCMB), Delanium, native graphite, lithium titanate, sodium titanate, nano-silicon, micron silicon, tin, antimony, germanium, transition metal oxide and above material surface are coated with carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer, carbonaceous mesophase spherules (MCMB), Delanium, native graphite, lithium titanate, sodium titanate, Na
0.66li
0.22ti
0.78o
2, nano-silicon, micron silicon, tin, antimony, germanium, a kind of or arbitrary proportion in transition metal oxide several.
Concrete, the method that battery pole piece carries out alkali metal is in advance: in an inert atmosphere or under vacuum environment, negative pole piece of battery is contacted with described alkali metal solution, after standing, cleaning, vacuumize, prepares pretreated negative pole piece of battery.
Wherein, preliminary treatment specifically refers to alkali metal in advance, and it is realized by haptoreaction, and concrete haptoreaction can be realized by following several aspect:
1, solution left standstill contact;
2, by shower nozzle spraying contact;
3, coated with Contact;
In addition, in the process that negative pole piece of battery contacts with described alkali metal solution, heat treated can also be carried out to described negative pole piece of battery and described alkali metal solution; Wherein, the temperature of described heat treated is 40 DEG C ~ 100 DEG C.
Preferably, in solution left standstill contact, time of contact is 5 seconds ~ 30 minutes;
Preferably, in shower nozzle spraying contact, described shower nozzle can be one or more of single spraying head and many shower nozzles; The nozzle of described shower nozzle can be one or more in metallic nozzle, plastic nozzle, ceramic nozzle and alloy nozzle; The nozzle of described shower nozzle can be one or more in annular, square, circular, oval, polygon and rhombus; In described shower nozzle spraying contact, spray speed is 0.05ml/s ~ 50ml/s;
Preferably, in coated with Contact, coating weight is 0.05ml/cm
2~ 10ml/cm
2.
The method of negative pole piece of battery being carried out to alkali metal in advance that the embodiment of the present invention 4 provides, carries out the alkali metal of the mode compensated in advance loss of reaction of pre-alkali metal by anticathode, greatly can improve head week efficiency and the energy density thereof of battery.
Below by embodiment 5 ~ embodiment 14, illustrate the performance of the battery of the negative pole piece of battery comprising alkali metal in advance prepared by the method that provides of the application embodiment of the present invention 4.
Embodiment 5
In the present embodiment, alkali metal solution is preferably lithiumation solution, and active material is preferably hard carbon, and conductive additive is preferably carbon black; By weight, hard carbon: carbon black: Kynoar (PVDF)=8:1:1 batching, prepares hard carbon cathode pole piece afterwards.Wherein alkali metal solution elects polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 0.3g/L as, and the lithiumation time is 60s.
The assembling of simulated battery carries out in the glove box containing high-purity Ar atmosphere, with lithium metal as to electrode, and the LiPF of 1 mole
6solution in the EC/DMC of 1L, as electrolyte, is assembled into battery.Use discharge and recharge instrument to carry out the test of constant current charge-discharge pattern, discharge cut-off voltage is 0.005V, and charge cutoff voltage is 2V, tests and carries out under C/3 current density.
Test result is shown in Fig. 2 and Fig. 3, wherein a, b, c, d are respectively first week discharge curve, first week charging curve, the tenth week discharge curve, the tenth week charging curve, compared by Fig. 2 with Fig. 3 and comparative example 1, can see that all efficiency of informing against brings up to 66% from 62%, successful, the cycle performance of lithium ion battery also can be kept preferably simultaneously.
Embodiment 6
In the present embodiment, alkali metal solution is preferably lithiumation solution, and active material is preferably hard carbon, and conductive additive is preferably carbon black; By weight, hard carbon: carbon black: Kynoar (PVDF)=8:1:1 batching, prepares hard carbon cathode pole piece afterwards.Wherein alkali metal solution elects polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 0.5g/L as, and the lithiumation time is 5s.
The assembling of simulated battery and test are with embodiment 5.
Test result is shown in Fig. 4 and Fig. 5, wherein a, b, c, d are respectively first week discharge curve, first week charging curve, the 5th week discharge curve, the 5th week charging curve, compared by Fig. 4 with Fig. 5 and ratio 1, can see that all efficiency of informing against brings up to 68% from 62%, successful, the cycle performance of lithium ion battery also can be kept preferably.
Embodiment 7
In the present embodiment, alkali metal solution is preferably lithiumation solution, and active material is preferably hard carbon, and conductive additive is preferably carbon black; By weight, hard carbon: carbon black: Kynoar (PVDF)=8:1:1 batching, prepares hard carbon cathode pole piece afterwards.Wherein alkali metal solution elects polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 0.5g/L as, and the lithiumation time is 60s.
The assembling of simulated battery and test are with embodiment 5.
Test result is shown in Fig. 6 and Fig. 7, wherein a, b, c, d are respectively first week discharge curve, first week charging curve, the 15 week discharge curve, the 15 week charging curve, compared by Fig. 6 with Fig. 7 and comparative example 1, can see that all efficiency of informing against brings up to 76% from 62%, successful, the cycle performance of lithium ion battery also can be kept preferably.
Embodiment 8
In the present embodiment, alkali metal solution is preferably lithiumation solution, and active material is preferably hard carbon, and conductive additive is preferably carbon black; By weight, hard carbon: carbon black: Kynoar (PVDF)=8:1:1 batching, prepares hard carbon cathode pole piece afterwards.Wherein alkali metal solution elects polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 2g/L as, and the lithiumation time is 60s.
The assembling of simulated battery and test are with embodiment 5.
Test result is shown in Fig. 8 and Fig. 9, wherein a, b, c, d be respectively first week discharge curve, first week charging curve, the 100 week discharge curve, hundred weeks Mondays charging curve, compared by Fig. 8 with Fig. 9 and comparative example 1, can see that all efficiency of informing against brings up to 90% from 62%, successful, the cycle performance of lithium ion battery also can obtain extraordinary maintenance.
Embodiment 9
In the present embodiment, alkali metal solution is preferably lithiumation solution, and active material is preferably hard carbon, and conductive additive is preferably carbon black; By weight, hard carbon: carbon black: Kynoar (PVDF)=8:1:1 batching, prepares hard carbon cathode pole piece afterwards.Wherein alkali metal solution elects polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 2g/L as, and the lithiumation time is 20s.
The assembling of simulated battery and test are with embodiment 5.
Test result is shown in Figure 10 and Figure 11, wherein a, b, c, d are respectively first week discharge curve, first week charging curve, the 15 week discharge curve, the 15 week charging curve, compared by Figure 10 with Figure 11 and comparative example 1, can see that all efficiency of informing against brings up to 98% from 62%, successful, the cycle performance of lithium ion battery also can be kept preferably.
Embodiment 10
In the present embodiment, described alkali metal solution is lithiumation solution, and active material is preferably carbon black, and by weight, carbon black: esterify pectin=8:2 batching, prepares carbon black cathode pole piece afterwards.Wherein lithiumation solution is preferably polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 2g/L, and the lithiumation time is 10s.
The assembling of simulated battery carries out in the glove box containing high-purity Ar atmosphere, with lithium metal as to electrode, and the LiPF of 1 mole
6solution in EC/DMC, as electrolyte, is assembled into battery.Use discharge and recharge instrument to carry out the test of constant current charge-discharge pattern, discharge cut-off voltage is 0.005V, and charge cutoff voltage is 2V, tests and carries out under 5C current density.
Test result is shown in Figure 12, and wherein a, b are respectively first week discharge curve, first week charging curve, are compared with comparative example 2 by Figure 12, can see that all efficiency of informing against brings up to 30% from 25%, successful.
Embodiment 11
In the present embodiment, described alkali metal solution is lithiumation solution, and active material is preferably carbon black, and by weight, carbon black: esterify pectin=8:2 batching, prepares carbon black cathode pole piece afterwards.Wherein lithiumation solution is preferably polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 2g/L, and the lithiumation time is 20s.
The assembling of simulated battery and test are with embodiment 10.
Test result is shown in Figure 13, and wherein a, b are respectively first week discharge curve, first week charging curve, are compared with comparative example 2 by Figure 13, can see that all efficiency of informing against brings up to 36% from 25%, successful.
Embodiment 12
In the present embodiment, described alkali metal solution is lithiumation solution, and active material is preferably carbon black, and by weight, carbon black: esterify pectin=8:2 batching, prepares carbon black cathode pole piece afterwards.Wherein lithiumation solution is preferably polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 2g/L, and the lithiumation time is 30s.
The assembling of simulated battery and test are with embodiment 10.
Test result is shown in Figure 14, and wherein a, b are respectively first week discharge curve, first week charging curve, is found out and comparative example 2 is compared by Figure 14, can see that all efficiency of informing against brings up to 45% from 25%, successful.
Embodiment 13
In the present embodiment, described alkali metal solution is lithiumation solution, and active material is preferably carbon black, and by weight, carbon black: esterify pectin=8:2 batching, prepares carbon black cathode pole piece afterwards.Wherein lithiumation solution is preferably polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 2g/L, and the lithiumation time is 60s.
The assembling of simulated battery and test are with embodiment 10.
Test result is shown in Figure 15 and Figure 16, wherein a, b, c, d are respectively first week discharge curve, first week charging curve, the kilocycle discharge curve, the kilocycle charging curve, compared by Figure 15 with Figure 16 and comparative example 2, can see that all efficiency of informing against brings up to 50% from 25%, successful, the cycle performance of lithium ion battery also can obtain extraordinary maintenance simultaneously.
Embodiment 14
In the present embodiment, described alkali metal solution is lithiumation solution, and active material is preferably nano-silicon, and by weight, nano-silicon: carbon black: esterify pectin=6:2:2 batching, prepares nano-silicon cathode pole piece afterwards.Wherein, lithiumation solution is preferably polycyclc aromatic compound-organic solvent lithiumation solution that concentration is 2g/L, and the lithiumation time is 60s.
The assembling of simulated battery carries out in the glove box containing high-purity Ar atmosphere, with lithium metal as to electrode, and the LiPF of 1 mole
6solution in EC/DMC, as electrolyte, is assembled into battery.Use discharge and recharge instrument to carry out the test of constant current charge-discharge pattern, discharge cut-off voltage is 0.005V, and charge cutoff voltage is 1V, tests and carries out under 0.1C current density.
Test result is shown in Figure 17 and Figure 18, wherein a, b are respectively first week discharge curve, first week charging curve, are compared by Figure 17 with Figure 18 and comparative example 3, can see that all efficiency of informing against brings up to 71% from 60%, successful, the cycle performance of lithium ion battery also can obtain extraordinary maintenance.
Comparative example 1
This comparative example is not for illustration of with by the performance of the battery pole piece of the method for alkali metal in advance of the present invention process.
In comparative example 1, the test condition of the choosing of active material, battery assembling process and battery is with embodiment 5, and difference is the method process that electrodes of lithium-ion batteries in this comparative example does not use alkali metal in advance.
Test result is shown in Figure 19 and Figure 20, and wherein a, b, c, d are respectively first week discharge curve, first week charging curve, the 100 week discharge curve, the 100 week charging curve.As can be seen from Figure 19 and Figure 20, its cycle performance is excellent, but first all coulombic efficiencies are very low, only have and are about 62%.
Comparative example 2
This comparative example is not for illustration of with by the performance of the battery pole piece of the method for alkali metal in advance of the present invention process.
In comparative example 2, the test condition of the choosing of active material, battery assembling process and battery is with embodiment 10, and difference is that electrodes of lithium-ion batteries in this comparative example is not with the method process of alkali metal in advance of the present invention.
Test result is shown in Figure 21 and Figure 22, and wherein a, b, c, d are respectively first week discharge curve, first week charging curve, the 10,000 week discharge curve, the 10,000 week charging curve.As can be seen from Figure 21 and Figure 22, its cycle performance is excellent especially, can stable circulation 10,000 weeks, but first all coulombic efficiencies are extremely low, only have and are about 28.9%.
Comparative example 3
This comparative example is not for illustration of with by the performance of the battery pole piece of the method for alkali metal in advance of the present invention process.
In comparative example 3, the test condition of the choosing of active material, battery assembling process and battery is with embodiment 14, and difference is that electrodes of lithium-ion batteries in this comparative example is not with the method process of alkali metal in advance of the present invention.
Test result is shown in Figure 23 and Figure 24, and wherein a, b are respectively first week discharge curve, first week charging curve.As seen from Figure 24, first all coulombic efficiencies are very low, only have and are about 60%.
Comprehensive above to consider, the present invention proposes that a kind of alkali metal ability is strong, the preparation method of the alkali metal solution of low price and environment-friendly and green, this solution can be utilized to carry out alkali metal in advance to battery electrode material.Concrete for non-lithium source positive electrode and the not high negative material of head week efficiency, propose the method to lithium ion battery electrode material preliminary treatment, simultaneously for the negative material pole piece that all efficiency of head is not high, propose the method to the preliminary treatment of battery electrode sheet.The method provided in the present invention's each embodiment above-mentioned all can use on a large scale, requires not harsh, can significantly reduce costs operating environment.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection range be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. a method for alkali metal in advance, it is characterized in that, described method comprises:
Under room temperature, in an inert atmosphere, be that the polycyclc aromatic compound of 0.005mol/L ~ 10mol/L is dissolved in organic solvent and forms precursor aqueous solution by concentration;
Alkali metal is added in described precursor aqueous solution;
Leave standstill 0.5 ~ 48 hour, described dissolved alkali metal, in precursor aqueous solution, forms the blackish green or lurid alkali metal solution of black; Wherein, in described alkali metal solution, alkali-metal content is 0.005g/L ~ 150g/L.
2. method according to claim 1, is characterized in that, described alkali metal be in Powdered, sheet, bar-shaped or band shape any one or multiple.
3. method according to claim 1, is characterized in that, described alkali metal comprise in lithium, sodium, potassium, rubidium, caesium, francium one or more.
4. method according to claim 1, is characterized in that, described polycyclc aromatic compound be specially in naphthalene, biphenyl, terphenyl, quaterphenyl, anthracene, phenanthrene and derivative thereof one or more.
5. method according to claim 1, is characterized in that, described organic solvent is specially dimethyl ether, diethyl ether, glycol dimethyl ether, butyl cellosolve, dibutyl ethylene glycol ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, one or more in propylene glycol diethyl ether.
6. method according to claim 1, is characterized in that, described alkali-metal content is 0.5g/L ~ 60g/L.
7. the alkali metal solution prepared as above-mentioned method according to claim 1 is for a preparation method for cell positive material, and it is characterized in that, described method comprises:
Described alkali metal solution is mixed with anode raw material, after standing, cleaning and filtering, vacuumize, prepares cell positive material;
Described anode raw material comprise: a kind of or arbitrary proportion of vanadic oxide, chromium three oxygen eight, ferric phosphate, cobalt oxide, LiMn2O4, nickel oxide, manganous oxide several.
8. the alkali metal solution prepared as above-mentioned method according to claim 1 is for the pretreated method of negative pole piece of battery, and it is characterized in that, described method comprises:
In an inert atmosphere or under vacuum environment, negative pole piece of battery being contacted with described alkali metal solution, through leaving standstill, cleaning, after vacuumize, preparing pretreated negative pole piece of battery.
9. method according to claim 8, is characterized in that, described contact is specially: solution left standstill contacts; Wherein, the time of contact of described alkali metal solution and described negative pole piece of battery is 5 seconds ~ 30 minutes.
10. method according to claim 8, is characterized in that, described contact is specially: shower nozzle spraying contact; Wherein, the spray speed of shower nozzle spraying is 0.05ml/s ~ 50ml/s.
11. methods according to claim 8, is characterized in that, described contact is specially: coated with Contact; Wherein, described alkali metal solution coat amount is 0.05ml/cm
2~ 10ml/cm
2.
12. methods according to claim 8, is characterized in that, in the process that described negative pole piece of battery contacts with described alkali metal solution, carry out heat treated to described negative pole piece of battery and described alkali metal solution; Wherein, the temperature of described heat treated is 40 DEG C ~ 100 DEG C.
13. methods according to claim 8, is characterized in that, described negative pole piece of battery is prepared by negative electrode active material;
Described negative electrode active material comprises: hard carbon, carbonaceous mesophase spherules MCMB, Delanium, native graphite, lithium titanate, nano-silicon, micron silicon, tin, antimony, germanium, transition metal oxide, and above material surface is coated with hard carbon, carbonaceous mesophase spherules MCMB, Delanium, native graphite, titanium oxide, lithium titanate, sodium titanate, the Na of carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer
0.66li
0.22ti
0.78o
2, nano-silicon, micron silicon, tin, antimony, germanium, a kind of or arbitrary proportion in transition metal oxide several.
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