CN109004229A - A kind of anode material for lithium-ion batteries additive and its positive electrode and lithium ion secondary battery - Google Patents

A kind of anode material for lithium-ion batteries additive and its positive electrode and lithium ion secondary battery Download PDF

Info

Publication number
CN109004229A
CN109004229A CN201810877700.7A CN201810877700A CN109004229A CN 109004229 A CN109004229 A CN 109004229A CN 201810877700 A CN201810877700 A CN 201810877700A CN 109004229 A CN109004229 A CN 109004229A
Authority
CN
China
Prior art keywords
lithium
additive
battery
positive electrode
conducting polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810877700.7A
Other languages
Chinese (zh)
Other versions
CN109004229B (en
Inventor
曾丹黎
张斌
孙玉宝
陈奇
刘光鹏
张俊峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Geosciences
Original Assignee
China University of Geosciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Geosciences filed Critical China University of Geosciences
Priority to CN201810877700.7A priority Critical patent/CN109004229B/en
Publication of CN109004229A publication Critical patent/CN109004229A/en
Application granted granted Critical
Publication of CN109004229B publication Critical patent/CN109004229B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of anode material for lithium-ion batteries additive and its positive electrode and lithium ion secondary batteries, belong to electrochemical technology field.Anode material for lithium-ion batteries additive of the invention is the conducting polymer monomeric unit containing carboxyl, prepares slurry together with binder, conductive agent and active material after the additive lithiumation, then prepare electrode slice, is assembled into battery.Such additive can carry out in-situ electrochemical polymerization by charge and discharge process in inside battery, form the more stable positive system of structure.Using additive of the invention, the conducting polymer of the carboxyl containing high concentration can be introduced in situ in inside battery, the LiFePO4 button cell impedance being assembled by the additive is small, shows higher specific capacity, better high rate performance and cyclical stability, have a good application prospect.

Description

A kind of anode material for lithium-ion batteries additive and its positive electrode and lithium ion secondary Battery
Technical field
The invention belongs to electrochemical technology fields, it is more particularly related to a kind of anode material for lithium-ion batteries Additive and the positive electrode of conducting polymer cladding is realized by the in-situ polymerization of the additive and by the positive electrode system Standby lithium ion secondary battery.
Background technique
Lithium ion battery energy density is high, and high-efficient, quality is relatively light, easy to carry, to become consumer electricity The main power source of sub- product.No matter academia or industry have put into a large amount of energy all to further increase lithium ion battery Performance, to meet all-electric automobile from now on, the demand of military field and space field.Although much having high capacity and height The new electrode materials of high rate performance are studied, but the performance of battery is still limited by conventional binders.It is conductive Lack mechanical bonding force between the mixture of phase and be random distribution, leads to electron-transport bottleneck and poor contact, hinder Effective contact to battery component.For ideal electrode, each active particle should reasonably shape, and disperse and be connected to Collector and solid or liquid electrolyte with low resistance and continuous inner track.Therefore, electronics and ion can be promoted to pass It is defeated, mechanical adhesion and flexibility, enhancing surface compatability and the novel binders system for improving active particle dispersibility are provided It develops especially important for next-generation high-energy, high power lithium ion cell.
Conventional binders show more serious in ultra-high capacity electrode biggish for volume change in electrochemical process The problem of.These electrode materials tend to produce the stress more much higher than graphite, lead to lead rupture and layering.As traditional double The improvement of component binder design, the polymer such as carboxymethyl cellulose (CMC) with high concentration carboxyl are poly- (acrylic acid) (PAA) and alginate is studied as new polymers binder in recent years.These polymer are changed by establishing chemical bond The surface of property active particle, to promote to be formed stable solid electrolyte interface film (SEI) between each phase and provide high resiliency mould Amount is to adapt to volume change, to substantially increase the stability of high-capacity electrode.
Carbonaceous additive is still extremely important in Bicomponent binder system, to improve the electric conductivity of positive electrode.Cause This, is recently proposed and has studied the one pack system multifunctional binder system based on conducting polymer, because electricity can be enhanced in they Sub- conductance and have the advantages that conventional polymer, therefore may be used as conductive additive and binder component.Different strategies are It is developed and changes its property and assign their other new functions.Multifunctional binder is designed by molecular modification, wherein Different functional groups is introduced on conducting polymer backbones to realize such as tunable electric conductivity, mechanical adhesion and electrolyte are inhaled The functions such as receipts.
According to features described above, the conducting polymer containing high concentration carboxyl functional group can be used as electrode multifunctional binder It is studied.General a large amount of synthesis conducting polymers use chemical oxidization method, common oxidant such as ferric ion (Fe3+), over cure acid group (S2O8 2-) etc. carry out oxidation polymerization, this method is needed using a large amount of oxidant (such as FeCl3, Generally use 4 times of equivalents), and yield is not high, lacks certain practicability.In addition, this method inevitably introduce it is miscellaneous Matter ion, and foreign ion is not easy to remove, and can have a certain impact to the performance of battery.Electrochemical polymerization is also a kind of synthesis The method of conducting polymer, this method advantage are to be swift in response, and do not introduce other metal ions, prepare resulting conducting polymer Purity is high, but complicated for operation and needs support electrolyte and high-purity solvent using a large amount of, and polymer is only in electrode table Face deposition, yield and efficiency are lower, are not suitable for largely preparing.
Summary of the invention
In order to overcome the shortcomings of the prior art described above, the present invention provides a kind of novel anode additive, original is utilized Position electrochemical polymerization can get the positive electrode of conducting high polymers object cladding.In addition, the content of present invention also include it is above-mentioned The method of the conducting high polymers object containing high concentration carboxyl is introduced in li-ion electrode materials and is prepared by the method Positive electrode and its lithium ion battery.
In common lithium-ion secondary cell system, positive electrode active materials (such as LiFePO 4, LiMn2O4, cobalt acid lithium And ternary material etc.) charging/discharging voltage be in 2.5~4.5V mostly (relative to Li+/ Li), and this section exactly corresponds to The voltage range of the conducting polymer conjugate unit such as electrochemically oxidative polymerization of thiophene, aniline, pyrroles etc. and its substituent. Therefore, the charge and discharge process of battery provides the necessary condition that such conjugate unit carries out electrochemical polymerization.I.e. in anode sizing agent The conjugative monomer of small molecule is added in preparation process, in-situ electrochemical polymerization is carried out by battery charge and discharge process to prepare conduction Polymer, different for the cladding and bonding of active material, and external directly addition polymer, the strategy of in-situ polymerization will be led Cause more effective polymer overmold and more stable electrode structure.
The first aspect of the invention provides a kind of anode material for lithium-ion batteries additive, and the additive is can The conjugate unit of electrochemical polymerization is carried out, the conjugate unit can carry out in-situ electrochemical polymerization in the battery.
Further, conjugate unit as described in the above technical scheme is thiophene, pyroles heterocyclic conducting polymer monomer Or any one of benzene, aniline, alkylbenzene, alkoxy benzene class aromatic series conducting polymer monomer, the structure of the conjugate unit Formula is shown in general formula one, general formula two or general formula three in formula one.
Further, conducting polymer monomer as described in the above technical scheme contains a carboxyl or multiple carboxyls.
It is further preferred that conducting polymer monomer as described in the above technical scheme is preferably 3- thiophene malonic acid, 3- Any one of thiophene acetic acid, N- pyrrole propanoic acid, 3- pyrrole carboxylic acid (see example 1~4), structure respectively as in formula two A, B, C, shown in D:
The second aspect of the invention provides the preparation of the anode material for lithium-ion batteries comprising additive described above Method, described method includes following steps:
(1) lithiumation of conducting polymer monomer: by the carboxyl and lithium hydroxide (LiOH) in the conducting polymer monomer The ratio between amount of substance according to 1:0.9 carries out lithiumation in aqueous solvent, and carboxyl lithiumation is made in solvent evaporated after the completion of lithiation Conducting polymer monomer afterwards；
(2) active material, conduction C powder, binder and additive are prepared into positive electrode together, then assemble electrode slice At button cell.Wherein: the additive is the conducting polymer monomer after carboxyl lithiumation made from step (1).
Further, above-mentioned technical proposal, on the basis of the total weight of positive electrode, the content of the additive is 1~ 10%.
Further, the content of additive as described in the above technical scheme is 5%.
Preferably, active material described in above-mentioned technical proposal is LiFePO 4 (LiFePO4), conductive C powder is acetylene Black, binder is Kynoar (PVDF).
It is further preferred that in above-mentioned technical proposal LiFePO 4, acetylene black, Kynoar, additive quality Than for 70:20:5:5.
Make conducting polymer monomer that electrochemical in-situ polymerization occur under 2.5~4.3V voltage conditions, obtains the present invention The positive electrode of the conducting polymer cladding.Reaction process is shown in attached drawing 1.
The third aspect of the invention, provides a kind of lithium ion secondary battery, and the lithium ion battery includes positive material Material, negative electrode material, electrolyte, diaphragm and battery case, the positive electrode are lithium ion cell positive material described above Material.
Compared with prior art, the invention has the following beneficial effects:
(1) conducting polymer of the invention is by the conducting polymer monomer (additive of the present invention) after lithiumation one Under fixed current potential, makes additive that in-situ electrochemical polymerization occur and be made.Present invention introduces the methods of conducting polymer simply, easily grasps Make, the impure ion of conductive polymeric binder for overcoming the synthesis of traditional chemical oxidizing process leads to lacking for battery performance reduction It falls into.
(2) conducting polymer of the invention can realize the in-stiu coating to active material, while may also function as the function of bonding Can, keep electrode structure more stable, is beneficial to the multiplying power and cycle performance of its battery.
(3) due to the presence of carboxylic acid lithium and the characteristic of conducting polymer, the material of such in-situ polymerization can not only conduct Lithium ion, and electronics can be conducted, so that the lithium ion battery containing the additive be made to can get more efficient ion/electronics Transmission；
(4) lithium ion battery assembled using additive of the invention is compared to additive-free lithium ion battery, battery Impedance is smaller, and specific discharge capacity is higher, and high rate performance is more preferable, and cyclical stability is also more preferable, and comprehensive performance is more excellent；
(5) the LiFePO4 button cell of additive of the invention, especially addition 3- thiophene malonic acid is shown more High capacity, better high rate performance and cyclical stability；
(6) the lithium ion battery excellent combination property being assembled into using additive of the invention, can be applied to just It takes in handheld electric products or electric vehicle, there are good market prospects.
Detailed description of the invention
Fig. 1 is the lithiumation and reaction process figure of additive in the embodiment of the present invention 1: with 3- thiophene malonic acid lithiumation first Two lithium (3TPMALi) of 3- thiophene malonic acid is obtained, then carries out electrochemical polymerization after assembled battery in battery charge and discharge process.
Fig. 2 is lithium ion battery the following under the conditions of sweeping speed and being 0.5mV/s that the embodiment of the present invention 1 and reference examples 1 make Ring volt-ampere curve comparison diagram.
Impedance curve pair of the Fig. 3 for the embodiment of the present invention 1 and the lithium ion battery of the production of reference examples 2 before circulating battery Than figure.
Impedance curve pair of the Fig. 4 for the embodiment of the present invention 1 and the lithium ion battery of the production of reference examples 2 after circulating battery Than figure.
Fig. 5 is the performance comparison figure for the lithium ion battery multiplying power that the embodiment of the present invention 1 and reference examples 2 make.
Cycle performance of battery pair of the Fig. 6 for the embodiment of the present invention 1 and the lithium ion battery of the production of reference examples 2 under 1C multiplying power Than figure.
Specific embodiment
Technical solution of the present invention is described in detail below by specific embodiment and attached drawing.Following reality Applying example is only preferred embodiments of the present invention, is not the restriction that other forms are done to the present invention, any skill for being familiar with this profession Art personnel are changed to the equivalent embodiment changed on an equal basis possibly also with the technology contents of the disclosure above.It is all without departing from this hair Bright plan content, any simple modification or equivalent variations made according to the technical essence of the invention to following embodiment, falls Within the scope of the present invention.
Embodiment 1
The present embodiment is a kind of anode material for lithium-ion batteries additive and its anode and lithium secondary battery, the additive For the conducting polymer monomeric unit containing high concentration carboxyl.This example selects 3- thiophene malonic acid (3TPA), and the reaction mechanism mechanism of reaction is such as Shown in Fig. 1.
The lithiation process of 3- thiophene malonic acid described above is specific as follows:
The lithiumation of 3- thiophene malonic acid: by 0.8618g (0.01mol) 3- thiophene malonic acid and 0.4800g (0.02mol) hydrogen Lithia (LiOH) carries out lithiumation in aqueous solvent, and the lithiumation time is 3 hours, after the completion of lithiation, and 3- is made in solvent evaporated Thiophene Lithium malonate (3TPMALi).
The anode material for lithium-ion batteries preparation step of the present embodiment is as follows:
By 0.1402g LiFePO 4 (LiFePO4), 0.0401g acetylene black, 0.0103g Kynoar (PVDF) and 0.0102g 3- thiophene Lithium malonate (3TPMALi) described above according to 70wt%, 20wt%, 5wt% and 5wt% ratio It is dissolved in N-Methyl pyrrolidone (NMP) and slurry is made, be coated on aluminium foil, the circular electric pole piece of 15mm diameter is cut into drying.
Positive electrode obtained above is assembled into CR2025 button cell, in which: cathode is metal lithium sheet, and diaphragm is poly- Propylene film (PP film), electrolyte solution are 1M LiPF6In EC/DMC (1:1, vol%).
Electrochemical polymerization: it is polymerize using cyclic voltammetry.With the sweep speed of 0.5mV/s, in 2.5~4.3V voltage Cyclic voltammetry scan is carried out in range, the 3- thiophene Lithium malonate (3TPMALi) can start to polymerize in 3.7V or so, arrive 4.3V Shi Juhe is complete.
Reference examples 1
The specific embodiment of this comparative example is to be assembled into button for the 3TPMALi of above-mentioned synthesis as the active material of anode Formula battery probes into the redox active of material itself.
The anode material for lithium-ion batteries preparation step of this comparative example is as follows:
By 0.0701g 3TPMALi, 0.0202g acetylene black, 0.0101g Kynoar (PVDF) according to 70wt%, The ratio of 20wt%, 10wt% are dissolved in N-Methyl pyrrolidone (NMP) and slurry are made, and are coated on aluminium foil, and it is straight to be cut into 15mm for drying The circular electric pole piece of diameter.
Positive electrode obtained above is assembled into CR2025 button cell, in which: cathode is metal lithium sheet, and diaphragm is poly- Propylene film (PP film), electrolyte solution are 1M LiPF6In EC/DMC (1:1, vol%).
Cyclic voltammetry curve test: with the sweep speed of 0.5mV/s, circulation volt is carried out in 2.5~4.3V voltage range Peace scanning, the 3TPMALi can start oxidation polymerization in 3.7V or so, and oxidation polymerization is complete when arriving 4.3V.Whole process does not have There is redox invertibity.
Reference examples 2
This comparative example specific embodiment is not add the lithium acid lithium iron battery of the 3TPMALi of above-mentioned synthesis and be added to 3- The lithium acid lithium iron battery of thiophene Lithium malonate carries out the comparison of redox property.
The anode material for lithium-ion batteries preparation step of this comparative example is as follows:
By 0.0703g LiFePO 4 (LiFePO4), 0.0204g acetylene black, 0.0103g Kynoar (PVDF) is pressed According to 70wt%, the ratio of 20wt%, 10wt% are dissolved in N-Methyl pyrrolidone (NMP) and slurry are made, and are coated on aluminium foil, dry, It is cut into the circular electric pole piece of 15mm diameter.
Positive electrode obtained above is assembled into CR2025 button cell, in which: cathode is metal lithium sheet, and diaphragm is poly- Propylene film (PP film), electrolyte solution are 1M LiPF6In EC/DMC (1:1, vol%).
Cyclic voltammetry curve test: with the sweep speed of 0.5mV/s, circulation volt is carried out in 2.5~4.3V voltage range Peace scanning, the circulation for the normal lithium acid lithium iron battery that the lithium acid lithium iron battery for not adding 3- thiophene Lithium malonate is shown Volt-ampere curve.
Fig. 2 is lithium ion battery the following under the conditions of sweeping speed and being 0.5mV/s that the embodiment of the present invention 1 and reference examples 1 make Ring volt-ampere curve comparison diagram.Solid line is the cyclic voltammetry curve for the lithium ion battery that reference examples 1 make in Fig. 2, shows 3TPMALi Start electrochemical polymerization in 3.7V or so, and process has irreversibility；Dotted line is respectively the lithium that embodiment 1 makes in Fig. 2 The cyclic voltammetry curve of ion battery first lap and the second circle, first lap curve show battery in addition to normal ferric phosphate lithium cell The more oxidation of redox extra curvature process, illustrate that electrochemical polymerization has occurred in 3TPMALi in the battery；Second Circle curve shows that the electrochemical polymerization of 3TPMALi has been completed in first lap, and process does not have invertibity.
Impedance curve pair of the Fig. 3 for the embodiment of the present invention 1 and the lithium ion battery of the production of reference examples 2 before circulating battery Than figure.Comparison discovery is before circulating battery, the battery high frequency region semi-circular portions of the battery of embodiment 1 relative to reference examples 2 Diameter is smaller, i.e., Charge-transfer resistance is smaller.The Charge-transfer resistance of battery is 34 Ω, blank battery after addition 3TPMALi Charge-transfer resistance be 59 Ω, illustrate add 3TPMALi can significantly reduce battery charge transfger impedance, be conducive to lithium from Transmission of the son in battery charging and discharging, reduces the dynamics limitation in cell operations, and chemical property is optimised.
Impedance curve pair of the Fig. 4 for the embodiment of the present invention 1 and the lithium ion battery of the production of reference examples 2 after circulating battery Than figure；In battery after constant current charge-discharge test under 1C multiplying power, the battery charge transfger impedance of embodiment 1 or obvious 2 battery of reference examples, while the Charge-transfer resistance of two kinds of batteries all decreases, the possible reason is battery is in an inside Adjustment of formula stage, electrolyte become compact etc. in the infiltration of electrode interior, the distribution of electrode material and electrode structure and all draw Lead the factor of this result.
Fig. 5 is the performance comparison figure for the lithium ion battery multiplying power that the embodiment of the present invention 1 and reference examples 2 make；In figure, when again When rate is 0.2C, 0.5C, 1C, the battery discharge specific capacity of embodiment 1 is apparently higher than the battery of reference examples 2, and specific capacity declines Subtract all than more gentle；When multiplying power is 2C, all there is more apparent decline in the specific discharge capacity of two kinds of batteries；When multiplying power reaches When to 5C or more, two kinds of battery specific capacities all significantly decay, and the specific capacity numerical difference of the two is away from gradually becoming smaller.
Cycle performance of battery pair of the Fig. 6 for the embodiment of the present invention 1 and the lithium ion battery of the production of reference examples 2 under 1C multiplying power Than figure.The battery first discharge specific capacity of embodiment 1 is 168mAh g as seen from the figure-1, and the battery of comparative example 2 is put for the first time Electric specific capacity is 133mAh g-1, the battery first discharge specific capacity for adding 3TPMALi is higher by 35mAhg-1, it is because of additive Lithium ion deintercalation rate in battery work is accelerated, so that electrochemical reaction is more abundant.Before the battery for introducing additive Specific discharge capacity is unstable in cyclic process several times, and main cause is battery not yet completely into the state of activation, stable SEI Film is also not fully developed, and with the increase of cycle-index, battery tends towards stability state, and capacity curve becomes stable and capacity Conservation rate is stablized.It is 155mAh g after 300 circulations, adding the battery discharge specific capacity of 3TPMALi-1, capacity guarantor Holdup is 92.3%, and blank battery discharge specific capacity is 118mAh g-1, capacity retention ratio 88.7%.Using 3TPMALi as adding Adding the battery of agent, not only specific discharge capacity is higher, and capacity attenuation reduces in cyclic process, and migration resistance drops when lithium ion deintercalation It is low, LiFePO4 structure is destroyed and is reduced, to guarantee battery discharge specific capacity.
Embodiment 2
The present embodiment is a kind of anode material for lithium-ion batteries additive and its anode and lithium secondary battery, the additive For the conducting polymer monomeric unit containing high concentration carboxyl, 3- thiophene acetic acid monomer is specifically formed into 3- thiophene after lithiumation Lithium acetate, then polymerize by electrochemical in-situ and be made.The structural formula of the 3- thiophene acetic acid monomer such as the formula B institute in summary of the invention Show.
The lithiation process of 3- thiophene acetic acid monomer described above is specific as follows:
The lithiumation of 3- thiophene acetic acid monomer: by 1.4205g (0.01mol) 3- thiophene acetic acid monomer and 0.2403g (0.01mol) lithium hydroxide (LiOH) carry out lithiumation soluble in water, lithiumation time are 3 hours, after the completion of lithiation, are evaporated molten 3- thiophene acetic acid monomer is made in agent.
The anode material for lithium-ion batteries preparation step of the present embodiment is as follows:
By 0.1403g LiFePO 4 (LiFePO4), 0.0404g acetylene black, 0.0103g Kynoar (PVDF) and Pyrroles -3- lithium acetate described above is dissolved in N-Methyl pyrrolidone according to the ratio of 70wt%, 20wt%, 5wt% and 5wt% (NMP) slurry is made, is coated on aluminium foil, the circular electric pole piece of 15mm diameter is cut into drying.
Positive electrode obtained above is assembled into CR2025 button cell, in which: cathode is metal lithium sheet, and diaphragm is poly- Propylene film (PP film), electrolyte solution are 1M LiPF6In EC/DMC (1:1, vol%).
Electrochemical polymerization: it is polymerize using cyclic voltammetry.With the sweep speed of 0.5mV/s, in 2.5~4.3V voltage Cyclic voltammetry scan is carried out in range, the pyrroles -3- lithium acetate can start to polymerize in 3.7V or so, polymerize when to 4.3V Entirely.It is similar with 1 result of embodiment.
Embodiment 3
The present embodiment is a kind of anode material for lithium-ion batteries additive and its anode and lithium secondary battery, the additive For the conducting polymer monomeric unit containing carboxyl, N- pyrrole propanoic acid monomer is specifically formed into N- pyrrole propanoic acid after lithiumation Lithium, then polymerize by electrochemical in-situ and be made.The N- pyrrole propanoic acid monomer structure formula is as shown in formula C.
The lithiation process of N- pyrrole propanoic acid described above is specific as follows:
The lithiumation of N- pyrrole propanoic acid: by 1.3903g (0.01mol) N- pyrrole propanoic acid and 0.2401g (0.01mol) hydroxide Carry out lithiumation soluble in water, lithiumation time are 3 hours, after the completion of lithiation, and N- pyrrole propanoic acid lithium is made in solvent evaporated.
The anode material for lithium-ion batteries preparation step of the present embodiment is as follows: by 0.1402g LiFePO 4 (LiFePO4), 0.0402g acetylene black, 0.0104g Kynoar (PVDF) and 0.0102g N- pyrrole propanoic acid described above Lithium is dissolved in N-Methyl pyrrolidone (NMP) according to the ratio of 70wt%, 20wt%, 5wt% and 5wt% and slurry is made, and is coated on Aluminium foil, drying, is cut into the circular electric pole piece of 15mm diameter.
Positive electrode obtained above is assembled into CR2025 button cell, in which: cathode is metal lithium sheet, and diaphragm is poly- Propylene film (PP film), electrolyte solution are 1M LiPF6In EC/DMC (1:1, vol%).
Electrochemical polymerization: it is polymerize using cyclic voltammetry.With the sweep speed of 0.5mV/s, in 2.5~4.3V voltage Cyclic voltammetry scan is carried out in range, the N- pyrrole propanoic acid lithium can start to polymerize in 3.6V or so, and polymerization is complete when arriving 4.3V. It is similar with 1 result of embodiment.
Embodiment 4
The present embodiment is a kind of anode material for lithium-ion batteries additive and its anode and lithium secondary battery, the additive For the conducting polymer monomeric unit containing carboxyl, 3- pyrrole carboxylic acid is specifically formed to 3- pyrrole carboxylic acid lithium after lithiumation, then It is made by electrochemical in-situ polymerization.The lithiation process of 3- pyrrole carboxylic acid described above is specific as follows:
The lithiumation of 3- pyrrole carboxylic acid: by 1.0802g (0.01mol) 3- pyrroles acetic acid and 0.2402g (0.01mol) hydroxide Lithium carry out lithiumation soluble in water, lithiumation time are 3 hours, after the completion of lithiation, and 3- pyrrole carboxylic acid lithium is made in solvent evaporated.
The anode material for lithium-ion batteries preparation step of the present embodiment is as follows:
By 0.1400g LiFePO 4 (LiFePO4), 0.0403g acetylene black, 0.0102g Kynoar (PVDF) and 0.0102g 3- pyrrole carboxylic acid lithium described above is dissolved in N- methyl according to the ratio of 70wt%, 20wt%, 5wt% and 5wt% Slurry is made in pyrrolidones (NMP), is coated on aluminium foil, and the circular electric pole piece of 15mm diameter is cut into drying.
Positive electrode obtained above is assembled into CR2025 button cell, in which: cathode is metal lithium sheet, and diaphragm is poly- Propylene film (PP film), electrolyte solution are 1M LiPF6In EC/DMC (1:1, vol%).
Electrochemical polymerization: it is polymerize using cyclic voltammetry.With the sweep speed of 0.5mV/s, in 2.5~4.3V voltage Cyclic voltammetry scan is carried out in range, the 3- pyrrole carboxylic acid can start to polymerize in 3.6V or so, and polymerization is complete when arriving 4.3V.With 1 result of embodiment is similar.

Claims (10)

1. a kind of anode material for lithium-ion batteries additive, it is characterised in that: the additive is that can carry out electrochemical polymerization Conjugate unit, the conjugate unit can carry out in-situ electrochemical polymerization in the battery.
2. anode material for lithium-ion batteries additive according to claim 1, it is characterised in that: the conjugate unit is Thiophene, pyroles heterocyclic conducting polymer monomer or benzene, aniline, alkylbenzene, alkoxy benzene class aromatic series conducting polymer monomer Any one of, the structural formula of the conjugate unit is shown in general formula one, general formula two or general formula three in formula one:
3. anode material for lithium-ion batteries additive according to claim 2, it is characterised in that: the conducting polymer Monomer contains a carboxyl or multiple carboxyls.
4. anode material for lithium-ion batteries additive according to claim 2, it is characterised in that: the conducting polymer Monomer is any one of 3- thiophene malonic acid, 3- thiophene acetic acid, N- pyrrole propanoic acid, 3- pyrrole carboxylic acid, and structure is respectively such as formula Shown in A, B, C, D in two:
5. a kind of preparation method of the anode material for lithium-ion batteries comprising any one of Claims 1 to 4 additive, special Sign is: described method includes following steps:
(1) lithiumation of conducting polymer monomer: by the carboxyl in the additive with lithium hydroxide (LiOH) according to the object of 1:0.9 The ratio between amount of matter carries out lithiumation, solvent evaporated after the completion of lithiation, the conducting polymer after carboxyl lithiumation is made in aqueous solvent Object monomer；
(2) by active material, conduction C powder, binder and positive electrode prepared by the additive after step (1) lithiumation together, so Electrode slice is assembled into button cell afterwards.
(3) charge and discharge are carried out for several times in 2.5~4.3V by the battery of step (2) preparation, after making conducting polymer monomer i.e. lithiumation Additive occur electrochemical in-situ polymerization.
6. the preparation method of positive electrode according to claim 5, it is characterised in that: using the total weight of positive electrode as base Standard, the content of the additive are 1~10%.
7. the preparation method of positive electrode according to claim 6, it is characterised in that: using the total weight of positive electrode as base Standard, the content of the additive are 5%.
8. the preparation method of positive electrode according to claim 5, it is characterised in that: the active material is ferrous phosphate Lithium (LiFePO4), conductive C powder is acetylene black, and binder is Kynoar (PVDF).
9. the preparation method of positive electrode according to claim 5, it is characterised in that: the LiFePO 4, acetylene black, Kynoar, additive mass ratio be 70:20:5:5.
10. a kind of lithium ion secondary battery, it is characterised in that: the lithium ion battery includes positive electrode, negative electrode material, electrolysis Liquid, diaphragm and battery case, the positive electrode are anode material for lithium-ion batteries made from claim 5 the method.
CN201810877700.7A 2018-08-03 2018-08-03 Lithium ion battery positive electrode material additive, positive electrode material thereof and lithium ion secondary battery Active CN109004229B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810877700.7A CN109004229B (en) 2018-08-03 2018-08-03 Lithium ion battery positive electrode material additive, positive electrode material thereof and lithium ion secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810877700.7A CN109004229B (en) 2018-08-03 2018-08-03 Lithium ion battery positive electrode material additive, positive electrode material thereof and lithium ion secondary battery

Publications (2)

Publication Number Publication Date
CN109004229A true CN109004229A (en) 2018-12-14
CN109004229B CN109004229B (en) 2021-07-13

Family

ID=64595174

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810877700.7A Active CN109004229B (en) 2018-08-03 2018-08-03 Lithium ion battery positive electrode material additive, positive electrode material thereof and lithium ion secondary battery

Country Status (1)

Country Link
CN (1) CN109004229B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110444766A (en) * 2019-08-14 2019-11-12 北京乐华锂能科技有限公司 A kind of tertiary cathode pole piece and the method for improving anode pole piece high temperature cyclic performance
CN111029158A (en) * 2019-12-22 2020-04-17 北京蒙京石墨新材料科技研究院有限公司 Lithium ion supercapacitor lithium pre-embedding method
CN111342130A (en) * 2020-03-04 2020-06-26 多氟多新能源科技有限公司 High-voltage-resistant lithium ion battery electrolyte matched with silicon-carbon cathode
CN112615046A (en) * 2020-11-27 2021-04-06 辽宁科技大学 Method for in-situ regulation and control of solid electrolyte interface layer of lithium battery
CN112885985A (en) * 2021-02-01 2021-06-01 中南大学 Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device
CN114420929A (en) * 2021-12-09 2022-04-29 万向一二三股份公司 Preparation method of solid battery containing conductive polymer binder
CN116613321A (en) * 2023-07-18 2023-08-18 宁德时代新能源科技股份有限公司 Composite cathode material, additive, cathode plate, secondary battery and electricity utilization device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104466135A (en) * 2014-12-15 2015-03-25 中信大锰矿业有限责任公司大新锰矿分公司 Method for coating conductive polymer on Ni-Co-Mn acid lithium positive electrode material
WO2016169398A1 (en) * 2015-04-22 2016-10-27 北京有色金属研究总院 In-situ crosslinking polymer binder for lithium-ion battery, and electrode manufactured by using same
CN106410165A (en) * 2016-11-30 2017-02-15 荆门市格林美新材料有限公司 Method for coating regenerated nickel-cobalt-manganese ternary battery electrode by in-situ electrochemical polymerization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104466135A (en) * 2014-12-15 2015-03-25 中信大锰矿业有限责任公司大新锰矿分公司 Method for coating conductive polymer on Ni-Co-Mn acid lithium positive electrode material
WO2016169398A1 (en) * 2015-04-22 2016-10-27 北京有色金属研究总院 In-situ crosslinking polymer binder for lithium-ion battery, and electrode manufactured by using same
CN106410165A (en) * 2016-11-30 2017-02-15 荆门市格林美新材料有限公司 Method for coating regenerated nickel-cobalt-manganese ternary battery electrode by in-situ electrochemical polymerization

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110444766A (en) * 2019-08-14 2019-11-12 北京乐华锂能科技有限公司 A kind of tertiary cathode pole piece and the method for improving anode pole piece high temperature cyclic performance
CN110444766B (en) * 2019-08-14 2021-09-21 创普斯(深圳)新能源科技有限公司 Ternary positive pole piece and method for improving high-temperature cycle performance of positive pole piece
CN111029158A (en) * 2019-12-22 2020-04-17 北京蒙京石墨新材料科技研究院有限公司 Lithium ion supercapacitor lithium pre-embedding method
CN111029158B (en) * 2019-12-22 2021-12-17 北京蒙京石墨新材料科技研究院有限公司 Lithium ion supercapacitor lithium pre-embedding method
CN111342130A (en) * 2020-03-04 2020-06-26 多氟多新能源科技有限公司 High-voltage-resistant lithium ion battery electrolyte matched with silicon-carbon cathode
CN112615046A (en) * 2020-11-27 2021-04-06 辽宁科技大学 Method for in-situ regulation and control of solid electrolyte interface layer of lithium battery
CN112615046B (en) * 2020-11-27 2023-11-21 辽宁科技大学 Method for in-situ regulation and control of solid electrolyte interface layer of lithium battery
CN112885985A (en) * 2021-02-01 2021-06-01 中南大学 Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device
CN114420929A (en) * 2021-12-09 2022-04-29 万向一二三股份公司 Preparation method of solid battery containing conductive polymer binder
CN114420929B (en) * 2021-12-09 2023-11-03 万向一二三股份公司 Preparation method of solid battery containing conductive polymer binder
CN116613321A (en) * 2023-07-18 2023-08-18 宁德时代新能源科技股份有限公司 Composite cathode material, additive, cathode plate, secondary battery and electricity utilization device

Also Published As

Publication number Publication date
CN109004229B (en) 2021-07-13

Similar Documents

Publication Publication Date Title
CN109004229A (en) A kind of anode material for lithium-ion batteries additive and its positive electrode and lithium ion secondary battery
CN101699590B (en) Hybrid supercapacitor
CN101207197B (en) Lithium ion battery anode material and lithium ion battery and anode containing the material
CN109390563B (en) Modified lithium iron phosphate positive electrode material, preparation method thereof, positive plate and lithium secondary battery
CN102637894B (en) Secondary battery with non-aqueous electrolyte
CN102598367B (en) Negative electrode for lithium secondary battery and manufacture method thereof
CN106797018B (en) Artificially synthesized SEI cathode material and lithium secondary battery comprising the same
CN101111954A (en) Positive electrode material for lithium secondary cell
CN103682356A (en) Lithium ion battery anode material and preparation method thereof
CN102280656A (en) Preparation method of lithium ion battery with positive electrode covered by conductive polymer
CN101478039B (en) Preparation for polypyrole coated lithium iron phosphate
CN106803574B (en) Anode material for lithium-ion batteries and its preparation method and application
CN102244233B (en) Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate
CN102593424A (en) Method for preparing anode of lithium ion battery
CN107768667B (en) Low-temperature circulating lithium iron phosphate power battery and preparation method thereof
CN108232161A (en) A kind of full battery of sodium ion
CN104170130A (en) Cathode active material composition and lithium secondary battery comprising same
CN111129457A (en) Aqueous ternary cathode slurry and preparation method thereof
CN104393291B (en) A kind of vanadium phosphate cathode material of doping, cladding modification altogether and preparation method thereof
CN112599859A (en) Preparation method of high-energy-density power battery
CN114122391A (en) High-power graphite composite material and preparation method thereof
CN101774563A (en) High-voltage positive electrode material used by lithium ion battery and preparation method thereof
CN114613974A (en) Long-life quick-charging type lithium ion battery cathode material and preparation method thereof
CN103000385A (en) Super hybrid capacitance battery and preparation method thereof
CN106953073A (en) Iron phosphate lithium positive pole composite and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant