CN112863898A - Lithium supplement additive for positive electrode of lithium ion capacitor and application of lithium supplement additive - Google Patents
Lithium supplement additive for positive electrode of lithium ion capacitor and application of lithium supplement additive Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a lithium supplement additive for a lithium ion capacitor anode and application thereof. The invention relates to a lithium supplement additive for a positive electrode of a lithium ion capacitor, which is lithium hydride dissolved in an ether solvent. According to the lithium supplement additive, lithium hydride powder is dissolved in an ether solvent, then the lithium hydride powder is dripped on a prepared electrode containing a positive active material, the solvent is removed, the lithium hydride powder is used as a positive electrode and assembled with a negative electrode to form a lithium ion super capacitor, and lithium supplement on the negative electrode of the lithium ion super capacitor is realized through first-loop discharge. Compared with the existing lithium supplement additive, the lithium hydride has ultrahigh theoretical specific capacity (3350mAh/g), can be dissolved in an ether solvent, can be directly dripped on a prepared positive plate when in use, and does not need to consider the compatibility problem of the lithium hydride and the solvent used for preparing positive plate slurry.
Description
Technical Field
The invention relates to a lithium supplement additive for a lithium ion capacitor anode, belonging to the technical field of electrochemical energy storage.
Background
In recent years, an electrochemical hybrid supercapacitor including an electric double layer capacitor electrode and a secondary battery electrode, in which a carbon material for storing energy by forming an electric double layer by interfacial charge adsorption and desorption is used as a positive electrode and a metal oxide or lithium intercalation carbonaceous material for storing energy by lithium ion intercalation/deintercalation is used as a negative electrode, has been a focus of research and development. Since the energy storage mechanism of the negative electrode is the same as that of the lithium ion battery system, it is also called: lithium ion super capacitor. Generally, in a lithium ion supercapacitor system, for a lithium intercalation negative electrode, certain irreversible lithium intercalation exists in the first charge and discharge process, and the electrochemical behavior can cause irreversible adsorption of electrolyte anions with the same molar number on the surface of an active carbon positive electrode, and finally, the reduction of the electrolyte ion concentration and the attenuation of the electrode capacity are caused, so that the charge and discharge performance of the lithium ion supercapacitor system is influenced. The problems can be solved by pre-embedding lithium into the negative electrode to a certain depth, and simultaneously, the lithium embedding potential of the negative electrode can be reduced and the reduced potential can be kept all the time, so that the charge and discharge performance of the lithium ion super capacitor, such as efficiency, cycling stability, large-current charge and discharge characteristics, and the like, can be improved.
At present, the method for pre-embedding lithium into the negative electrode mainly comprises the following steps: the lithium is pre-intercalated into the negative electrode by means of an external short circuit with metallic lithium as the third electrode, which has a number of disadvantages: firstly, the introduction of metal as one pole into the lithium ion capacitor system can cause safety problems; secondly, the battery assembly manufacturing process is complex and has strict requirements on the environment; thirdly, the lithium insertion process of the external short circuit is not easy to control; finally, lithium ion container systems require nearly one-fold addition of electrolyte, separator, etc. for pre-intercalation.
In addition, it has also been reported to incorporate additives (i.e., lithium-rich compounds with certain irreversible delithiation properties, such as Li) into the positive electrode2S/Co、Li2O/Co、LiF/Co、Li2C2、Li5FeO4、LiMO2Where M is Co, Ni, Mn, etc. and LiNixZ1-xO2Wherein Z is Mn, Co, Fe, La, V, Al, Mg, Zn, 0<x>1) The method of (1) pre-intercalating lithium into the negative electrode, has disadvantages of: as lithium in the lithium-rich compound is intercalated into the negative electrode, inactive products or unreacted lithium-rich compound are generated, and these substances remain in the positive electrode and affect the electrochemical performance of the lithium-ion supercapacitor. Although the positive electrode additive Li3N and Li2O2No residual substance is generated after the negative electrode is pre-embedded with lithium, but the use of the negative electrode and the negative electrode is limited, lithium nitride reacts with a solvent commonly used for preparing electrode slurry and is insoluble in an organic solvent, and Li2O2The lithium removal is difficult, a catalyst is required, and a decomposition product O2Which is detrimental to the battery performance.
Disclosure of Invention
In order to solve the technical problems and realize lithium supplement on the cathode of the lithium ion super capacitor, the invention adopts the following technical scheme:
the invention provides a lithium supplement additive for a lithium ion capacitor anode, which is lithium hydride.
In another aspect, the invention provides a positive electrode for a lithium ion capacitor or a lithium ion battery, which comprises the above lithium supplement additive.
The invention also provides a preparation method of the anode, which comprises the following steps:
(1) preparing an electrode A containing a positive active material by adopting a homogenization method, wherein slurry of the homogenization method comprises a positive active material, a conductive agent, a binder and an organic solvent, and the prepared electrode is marked as a positive electrode A;
(2) dissolving the lithium supplement additive in an ether solvent to obtain a lithium supplement additive solution;
(3) and (3) coating the lithium supplement additive solution on the electrode A in the step (1), removing the ether solvent, and compacting to obtain the anode B. And directly dripping ether solution of the lithium supplement additive on the anode, removing the ether solvent, rolling the anode to obtain an anode B, wherein the anode B is the anode to be obtained in the invention, and assembling the anode B and the cathode into a lithium ion capacitor and charging the lithium ion capacitor to ensure that lithium in the additive in the anode is extracted and embedded into the cathode.
Based on the above technical scheme, preferably, the ether solvent is: at least one of ethylene glycol dimethyl ether, anisole, diethyl ether, petroleum ether, tetrahydrofuran, 1, 4-dioxane and 1, 3-dioxolane.
Based on the technical scheme, preferably, the mass fraction of the lithium supplement additive in the lithium supplement additive solution is 0.1-5 wt%.
Based on the technical scheme, preferably, the positive electrode A is prepared by adopting a homogenization method, and the slurry comprises a positive electrode material, a conductive agent and a binder; the positive electrode material is at least one of a porous carbon material or a conductive polymer; the conductive agent is at least one of Super p, acetylene black or carbon nano tubes; the organic solvent is at least one of N-methyl pyrrolidone and N, N-dimethylformamide; the binder is polyvinylidene fluoride (PVDF). In the positive electrode, an active material: conductive agent: 75-90:5-15:5-10 of binder; in the positive electrode, the mass of the lithium supplement additive is 1-10%, and the lithium supplement additive is more preferably 2-5 wt%.
Based on the technical scheme, preferably, the porous carbon material is one or more than two of activated carbon fiber, activated carbon powder, carbon nano tube and graphene; the conductive polymer is one or more of polyaniline, polyparaphenylene, polypyrrole, polythiophene and derivatives thereof.
The invention also provides a lithium ion capacitor, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises the lithium supplement additive or is the positive electrode.
Based on the above technical solution, preferably, the negative electrode includes a negative electrode material; the negative electrode material is one or more than two of soft carbon, hard carbon, graphite, mesocarbon microbeads, lithium titanium oxide composite compounds, silicon/carbon, tin dioxide and molybdenum oxide;
the electrolyte is an organic solution comprising at least one lithium salt; the lithium salt is LiClO4、LiPF6、LiBF4。
Based on the above technical scheme, preferably, the first charging condition of the lithium ion capacitor is constant current charging: the charging current is 0.01-3mA, the time is 30-200h, and under the condition, the lithium in the lithium supplement additive is extracted and enters the negative electrode. The pre-lithium intercalation with the depth of 30-80% is carried out on the negative electrode.
Advantageous effects
(1) The method comprises the steps of taking a porous carbon material (such as activated carbon fiber, activated carbon powder, carbon nano tube, graphene and the like) or a conductive polymer (such as polyaniline, poly-p-phenylene, polypyrrole, polythiophene and derivatives thereof and the like) as a positive electrode, taking a lithium-embeddable carbon material (such as soft carbon, hard carbon, graphite, mesocarbon microbeads and the like) or lithium-embeddable oxide (lithium titanium oxide composite, tin dioxide, molybdenum oxide and the like) as a negative electrode, and taking LiClO4、LiPF6、LiBF4In a lithium ion super capacitor system taking organic solution of lithium salt as electrolyte, a positive electrode additive lithium hydride is introduced to realize pre-lithium intercalation with the depth of 30-80% of a negative electrode, so that the problems of irreversible adsorption of negative ions on the positive electrode and reduction of ion concentration of an electrolyte body caused by irreversible lithium intercalation of the negative electrode are solved, and meanwhile, the specific energy of the lithium ion super capacitor is further improved.
(2) Firstly, preparing a positive electrode taking a porous carbon material or a conductive polymer as an active substance, then dripping a solution consisting of lithium hydride/ether solvent on the positive electrode, directly assembling the positive electrode and a negative electrode into a lithium ion super capacitor after removing the ether solvent, and realizing pre-lithium intercalation of the negative electrode in the activation process of the first circle of the lithium ion super capacitor. Compared with the prior art, the product obtained by the irreversible delithiation of the cathode by the cathode additive lithium hydride is hydrogen, and is stored in an air bag reserved in the battery.
(3) In the prior art, most of the positive electrode lithium supplement additives are added into positive electrode active substances, conductive agents and binder slurry and blade-coated on a current collector to prepare a positive electrode, so that the positive electrode lithium supplement additives in the electrode are difficult to delithiate or vacancies are left in the positive electrode after delithiation, thereby influencing the structure of the positive electrode and finally causing poor cycle stability of the positive electrode. The positive electrode lithium supplement additive is dissolved in an ether solvent and then is dripped on an electrode containing a positive electrode active substance, namely the positive electrode lithium supplement additive is distributed on the surface of the electrode containing the positive electrode active substance, so that lithium can be easily removed without influencing the positive electrode structure and the cycle stability thereof
(4) The positive electrode lithium supplement additive has ultrahigh theoretical specific capacity (3350mAh/g), so that more lithium is extracted in the charging process, and compared with the prior art (the adopted theoretical capacity of the lithium supplement additive is only 150-800mAh/g, such as Li)2NiO2The exerted capacity is 340mAh/g), the addition amount can be less, and the high-efficiency lithium supplement can be achieved.
(5) The positive electrode lithium supplement additive is distributed on the surface of an electrode, and lithium is easy to remove and is embedded into a negative electrode after a certain current is applied; meanwhile, the lithium supplement additive is dissolved in the ether solvent and then is dripped on the electrode containing the positive active material, so that the problem of compatibility of the lithium supplement additive and a homogenizing solvent is not required to be considered.
(6) Positive electrode lithium supplement additive Li in prior art2MoO3And Li5FeO4Li/Li at very high potentials (4.7V vs. Li)+) Can remove lithium, the high potential can cause the decomposition of the electrolyte of the conventional battery to influence the performance of the battery, and the lithium removal potential of the lithium hydride of the anode lithium supplement additive is 4.0V vs+/Li。
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
Comparative example 1
Respectively preparing an active carbon anode and a hard carbon cathode by a homogenization method, and preparing the anodeThe mixture ratio is active carbon: conductive agent Super P: the mass ratio of the binder PVDF is 8:1:1, the negative electrode mixture ratio is hard carbon: conductive agent Super P: the mass ratio of the binder PVDF is 85:9: 6. Cutting the positive and negative electrodes into 2 × 2cm electrode plates, using active carbon as the positive electrode, hard carbon as the negative electrode, and 1M LiPF6DEC (volume ratio 1:1) is used as electrolyte, cellgard2400 is used as a diaphragm to assemble a soft-package lithium ion super capacitor, and the voltage interval of the capacitor is 2.8-4.2V.
Comparative example 2
Respectively preparing an active carbon anode and a hard carbon cathode by adopting a homogenization method, wherein the anode comprises the following components in percentage by weight: li2NiO2: conductive agent Super P: the mass ratio of the binder PVDF is 25:55:10:10, the negative electrode mixture ratio is hard carbon: conductive agent Super P: the mass ratio of the binder PVDF is 85:9: 6. Cutting the positive and negative electrodes into 2 × 2cm electrode sheets and coating with AC-Li2NiO2The positive electrode is made of hard carbon, the negative electrode is made of 1M LiPF6/EC: DEC (volume ratio of 1:1) as electrolyte, and the cellgard2400 is a diaphragm to assemble the soft-package lithium ion supercapacitor. Through the activation of the first circle, pre-lithium intercalation with the depth of 70% is realized on the negative electrode (the pre-lithium intercalation depth of 70% is the ratio of the pre-lithium intercalation capacity to the theoretical capacity of the negative electrode, the same is carried out below), and the voltage interval of the capacitor is 2.8-4.2V.
Comparative example 3
Respectively preparing an active carbon anode and a hard carbon cathode by adopting a homogenization method, wherein the anode comprises the following components in percentage by weight: li5FeO4: conductive agent Super P: the mass ratio F of the binder PVD is 55:25:10:10, the negative electrode mixture ratio is hard carbon: conductive agent Super P: the mass ratio of the binder PVDF is 85:9: 6. Cutting the positive and negative electrodes into 2 × 2cm electrode sheets and coating with AC-Li5FeO4The positive electrode is made of hard carbon, the negative electrode is made of 1M LiPF6/EC: DEC (volume ratio of 1:1) as electrolyte, and the cellgard2400 is a diaphragm to assemble the soft-package lithium ion supercapacitor. Through the activation of the first circle, pre-lithium intercalation with the depth of 70% is realized on the negative electrode, and the voltage interval of the capacitor is 2.8-4.7V.
Comparative example 4
Respectively preparing an active carbon anode and a hard carbon cathode by adopting a homogenization method, wherein the anode comprises the following components in percentage by weight: LiF/Co: conductive agent Super P: the mass ratio of the binder PVDF is 45:35:10:10, the negative electrode mixture ratio is hard carbon: conductive agent Super P: the mass ratio of the binder PVDF is 85:9: 6. Cutting the positive electrode and the negative electrode into 2 × 2 cm-sized electrode plates, and assembling the soft-package lithium ion super capacitor by using AC-LiF/Co as the positive electrode, hard carbon as the negative electrode, 1M LiPF6/EC: DEC (volume ratio of 1:1) as electrolyte and cellgard2400 as a diaphragm. Through the activation of the first circle, pre-lithium intercalation with the depth of 70% is realized on the negative electrode, and the voltage interval of the capacitor is 2.8-4.2V.
Example 1
Preparing a lithium hydride/diethyl ether solution with the mass fraction of 0.1 wt%. Respectively preparing an active carbon anode and a hard carbon cathode by adopting a homogenization method, wherein the anode comprises the following components in percentage by weight: conductive agent Super P: the mass ratio of the binder PVDF is 8:1:1, the negative electrode mixture ratio is hard carbon: conductive agent Super P: the mass ratio of the binder PVDF is 85:9: 6. Cutting the positive electrode and the negative electrode into electrode plates with the size of 2 x 2cm, repeatedly dripping the prepared lithium hydride/ether solution on the positive electrode plate (at the moment, the positive electrode is marked as AC-LiH), rolling and compacting the positive electrode plate after the ether solvent is naturally volatilized, and determining the amount of the lithium hydride by weighing the mass change of the positive electrode plate (before and after dripping the lithium hydride solution), wherein the mass fraction of the lithium hydride in the electrode is 1%. The mass fraction of lithium hydride in the electrode was 1%. And (2) assembling the soft-package lithium ion super capacitor by using AC-LiH as a positive electrode, hard carbon as a negative electrode, 1M LiPF6/EC: DEC (volume ratio of 1:1) as an electrolyte and cellgard2400 as a diaphragm. Through the activation of the first circle, the charging current is 0.05mA, the charging cut-off voltage is 4.2V, 35% of pre-embedded lithium is realized for the negative electrode, and the voltage interval of the capacitor is 2.8-4.2V.
Example 2
Preparing a lithium hydride/diethyl ether solution with the mass fraction of 2 wt%. Respectively preparing an active carbon anode and a hard carbon cathode by adopting a homogenization method, wherein the anode comprises the following components in percentage by weight: conductive agent Super P: the mass ratio of the binder PVDF is 8:1:1, the negative electrode mixture ratio is hard carbon: conductive agent Super P: the mass ratio of the binder PVDF is 85:9: 6. Cutting the positive electrode and the negative electrode into electrode plates with the size of 2 x 2cm, repeatedly dripping the prepared lithium hydride/ether solution on the positive electrode plate (at the moment, the positive electrode is marked as AC-LiH), rolling and compacting the positive electrode plate after the ether solvent is naturally volatilized, and determining the amount of the lithium hydride by weighing the mass change of the positive electrode plate (before and after dripping the lithium hydride solution), wherein the mass fraction of the lithium hydride in the electrode is 2%. And (2) assembling the soft-package lithium ion super capacitor by using AC-LiH as a positive electrode, hard carbon as a negative electrode, 1M LiPF6/EC: DEC (volume ratio of 1:1) as an electrolyte and cellgard2400 as a diaphragm. Through the activation of the first circle, the charging current is 0.05mA, the charging cut-off voltage is 4.2V, pre-lithium embedding with the depth of 70% is realized on the negative electrode, and the voltage interval of the capacitor is 2.8-4.2V.
Example 3
Preparing a lithium hydride/diethyl ether solution with the mass fraction of 3 wt%. Respectively preparing an active carbon anode and a hard carbon cathode by adopting a homogenization method, wherein the anode comprises the following components in percentage by weight: conductive agent Super P: the mass ratio of the binder PVDF is 8:1:1, the negative electrode mixture ratio is hard carbon: conductive agent Super P: the mass ratio of the binder PVDF is 85:9: 6. Cutting the positive electrode and the negative electrode into electrode plates with the size of 2 x 2cm, repeatedly dripping the prepared lithium hydride/ether solution on the positive electrode plate (at the moment, the positive electrode is marked as AC-LiH), rolling and compacting the positive electrode plate after the ether solvent is naturally volatilized, and determining the amount of the lithium hydride by weighing the mass change of the positive electrode plate (before and after dripping the lithium hydride solution), wherein the lithium hydride accounts for 3% in the electrode. And (2) assembling the soft-package lithium ion super capacitor by using AC-LiH as a positive electrode, hard carbon as a negative electrode, 1M LiPF6/EC: DEC (volume ratio of 1:1) as an electrolyte and cellgard2400 as a diaphragm. Through the activation of the first circle, the charging current is 0.05mA, the charging cut-off voltage is 4.2V, pre-lithium embedding with the depth of 80% is realized on the negative electrode, and the voltage interval of the capacitor is 2.8-4.2V.
Analysis of Experimental results
As can be seen from the results of the tests of examples 1-3 and comparative example (Table 1 below), it can be seen that the beneficial results of the present invention are: the purpose of pre-embedding lithium into the negative electrode can be realized by dripping a lithium supplement additive, namely a lithium hydride-containing solution, on the surface of the positive electrode, so that the capacity of the actual positive electrode is obviously improved, and the specific energy and the cycling stability of the whole battery are obviously improved. The positive electrode lithium supplement additives adopted in comparative examples 2-4 generate inactive substances to remain in the positive electrode after the first circle of lithium removal, thereby influencing the capacity exertion and the cycling stability of the positive electrode and further influencing the energy of the lithium ion super capacitorDensity and cycle stability. The lithium replenishment additive in comparative example 3 needs to be at a higher potential (4.7V vs. Li/Li)+) Lithium can be removed, and the high potential can cause the decomposition of the common electrolyte, thereby having adverse effect on the performance of the lithium ion super capacitor. In the prior art, the anode lithium supplement additive is distributed in the anode (surface and bulk phase), while in the invention, the anode lithium supplement additive is distributed on the surface of the anode, so that the lithium is shorter in a releasing path and is easier to release and embed into the cathode.
TABLE 1
Claims (10)
1. A lithium supplement additive for a lithium ion capacitor or a lithium ion battery anode is characterized in that: the lithium supplement additive is lithium hydride.
2. A positive electrode for a lithium ion capacitor or a lithium ion battery, characterized in that: comprising the lithium supplement additive of claim 1.
3. A method for producing the positive electrode according to claim 2, comprising the steps of:
(1) preparing an electrode A by adopting a homogenization method, wherein slurry of the homogenization method comprises a positive active material, a conductive agent, a binder and an organic solvent;
(2) dissolving the lithium supplement additive in an ether solvent to obtain a lithium supplement additive solution;
(3) before assembling the whole battery, coating the lithium supplement additive solution on the anode A, removing the ether solvent, and compacting to obtain the anode.
4. The process according to claim 3, wherein the ethereal solvent is: at least one of ethylene glycol dimethyl ether, anisole, diethyl ether, petroleum ether, tetrahydrofuran, 1, 4-dioxane and 1, 3-dioxolane.
5. The method of claim 3, wherein: in the lithium supplement additive solution, the mass fraction of the lithium supplement additive is 0.1-5 wt%.
6. The production method according to claim 3, wherein the positive electrode active material is at least one of a porous carbon material or a conductive polymer; the conductive agent is at least one of conductive carbon black (Super p), acetylene black or carbon nano tubes; the binder is polyvinylidene fluoride (PVDF); the organic solvent is at least one of N-methyl pyrrolidone and N, N-dimethylformamide; in the positive electrode, the mass ratio of an active material, a conductive agent and a binder is 75-90:5-15: 5-10; in the positive electrode, the mass of the lithium supplement additive is 1-10%.
7. The method according to claim 6, wherein the porous carbon material is one or more of activated carbon fiber, activated carbon powder, carbon nanotube, and graphene; the conductive polymer is one or more of polyaniline, polyparaphenylene, polypyrrole, polythiophene and derivatives thereof.
8. A lithium ion capacitor or a lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the lithium supplement additive according to claim 1 or the positive electrode is the positive electrode according to claim 2.
9. The lithium ion capacitor or battery of claim 8, wherein the negative electrode comprises a negative electrode material; the negative electrode material is one or more than two of soft carbon, hard carbon, graphite, mesocarbon microbeads, lithium titanium oxide composite compounds, silicon/carbon, tin dioxide and molybdenum oxide;
the electrolyte is an organic solution comprising at least one lithium salt; the lithium salt is LiClO4、LiPF6、LiBF4。
10. The lithium-ion capacitor or the lithium-ion battery according to claim 8, wherein the first charging condition of the lithium-ion capacitor is constant current charging: the charging current is 0.01-3mA, the charging cut-off voltage is 4.2V, and under the condition, the lithium in the lithium supplement additive is extracted and enters the negative electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114613614A (en) * | 2022-04-11 | 2022-06-10 | 浙江浙能技术研究院有限公司 | All-solid-state lithium ion capacitor and preparation method thereof |
| CN114824168A (en) * | 2022-04-14 | 2022-07-29 | 北京航空航天大学 | Lithium supplement agent and method for lithium ion battery anode, anode plate, lithium supplement slurry and battery |
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| CN114824168A (en) * | 2022-04-14 | 2022-07-29 | 北京航空航天大学 | Lithium supplement agent and method for lithium ion battery anode, anode plate, lithium supplement slurry and battery |
| CN114824168B (en) * | 2022-04-14 | 2023-10-20 | 北京航空航天大学 | Lithium supplementing agent for positive electrode of lithium ion battery, lithium supplementing method, positive electrode plate, lithium supplementing slurry and battery |
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