CN106058149B - Electrode slice and preparation method thereof and sodium-ion battery - Google Patents
Electrode slice and preparation method thereof and sodium-ion battery Download PDFInfo
- Publication number
- CN106058149B CN106058149B CN201610329954.6A CN201610329954A CN106058149B CN 106058149 B CN106058149 B CN 106058149B CN 201610329954 A CN201610329954 A CN 201610329954A CN 106058149 B CN106058149 B CN 106058149B
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- electrode material
- collector
- weight
- electrode slice
- 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.)
- Active
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/139—Processes of manufacture
-
- 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 field of batteries, disclose a kind of electrode slice, which includes: sealant, collector and negative electrode material, and the sealant is configured in the one side of the collector to seal the face, and the negative electrode material is configured in the hole of the collector；Wherein, the negative electrode material contains calcium containing compound, and the calcium containing compound of 50 weight % or more is Ca2N.The present invention also provides a kind of preparation method of electrode slice and electrode slices obtained by this method.The present invention also provides a kind of sodium-ion batteries.By using electrode slice of the invention, the high sodium-ion battery of specific discharge capacity can be obtained, it can be achieved that the reversible charge and discharge of height ratio capacity.
Description
Technical field
The present invention relates to field of batteries, and in particular, to a kind of electrode slice and preparation method thereof and sodium-ion battery.
Background technique
It exploits energetically and brings lack of energy and environmental pollution two greatly to mankind nowadays society using traditional fossil energy
Problem also forces people to accelerate the development and utilization of cleaning, renewable energy.Currently, using wind energy, solar energy, tide energy,
The power generations such as thermal energy be it is a kind of realize sustainable, environmentally protective development pattern, and energy storage device is realized randomness, intermittence
Renewable and clean energy resource be converted into electric energy and avoid to power grid generate impact key.Therefore, it develops the economy efficient energy storage
Technology becomes the research hotspot of researcher all over the world.
Lithium ion battery is one of the energy storage device for occupying leading position currently on the market, has energy density height, circulation
Service life length, memory-less effect, the advantages that self discharge is small, operating temperature range is wide.With mobile phone, laptop, tablet computer
The at full speed of equal electronic equipments popularize, and electric car, hybrid electric vehicle are greatly developed, and the demand of lithium ion battery is caused constantly to increase
Greatly.The price of lithium, which constantly increases, reserves constantly reduce becomes batch production lithium ion battery, applies lithium in energy-accumulating power station
The bottleneck of ion battery.
Compared to lithium resource, sodium energy storage very abundant, the reserves in the earth's crust are about 2.64%, occupy the 6th, and are distributed wide
It is general, refine it is simple, meanwhile, sodium and lithium have physicochemical properties similar with lithium and storage in the same main group of the periodic table of elements
Deposit mechanism.Therefore, the room temperature sodium-ion battery technology that development is directed to extensive stored energy application has own strategic significance.However
Due to sodium ion ionic radius (0.102nm) than lithium ion ionic radius (0.076nm) greatly, sodium ion is in electrode material
In deintercalation it is more difficult than lithium ion, cause most of li-ion electrode materials when for sodium-ion battery due to volume expansion
Cause structure collapses without can be carried out multiple circulation.
Summary of the invention
The purpose of the present invention is to provide one kind, and preferable specific discharge capacity and reversible can be obtained in sodium-ion battery
Electrode slice of specific discharge capacity and preparation method thereof and sodium-ion battery.
To achieve the goals above, the present invention provides a kind of electrode slice, which includes: sealant, collector and bear
Pole material, the sealant are configured at the face that the collector is sealed in the one side of the collector, the cathode material
Material is configured in the hole of the collector；The negative electrode material contains calcium containing compound, and the described of 50 weight % or more contains
Calcium compound is Ca2N。
The present invention also provides a kind of preparation methods of electrode slice, this method comprises:
(1) conductive agent and binder solution are mixed, sealing slurry is made；
(2) slurry will be sealed to be coated in the one side of collector, and dry, the afflux in one side with sealant is made
Body；
(3) negative electrode material will be inserted in the hole of step (2) resulting collector；
(4) collector obtained by pressing step (3)；
Wherein, the negative electrode material contains calcium containing compound, and the calcium containing compound of 50 weight % or more is Ca2N。
The present invention also provides electrode slices prepared by the above method.
The present invention also provides a kind of sodium-ion batteries, wherein the cathode of the sodium-ion battery is above-mentioned electrode slice.
By using electrode slice of the invention, the high sodium-ion battery of specific discharge capacity can be obtained, it can be achieved that Fabrication of High Specific Capacitance
Measure reversible charge and discharge.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of electrode slice, which includes: sealant, collector and negative electrode material, the sealant
It is configured in the one side of the collector to seal the face, the negative electrode material is configured in the hole of the collector；It is described
Negative electrode material contains calcium containing compound, and the calcium containing compound of 50 weight % or more is Ca2N。
According to the present invention, by Ca2N is configured in collector, and forms electrode slice, can be properly by Ca2N is applied to sodium
Negative electrode material is used as in ion battery, to obtain the sodium-ion battery of specific discharge capacity and reversible discharge specific capacity, preferable case
Under, preferably the calcium containing compound of 80 weight % or more is Ca2N, the calcium containing compound of more preferable 90 weight % or more
For Ca2The calcium containing compound of N, more preferable 95 weight % or more are Ca2N, the most preferably described calcium containing compound are Ca2N.To the greatest extent
Managing the negative electrode material can also be containing some additive of this field routine it should be appreciated that the calcic chemical combination
Object is existing for the active material as the negative electrode material, other have no effect on the performances such as the electrical property of the calcium containing compound
Conventional additives can be used as the adjunct ingredient of the negative electrode material, certainly, most preferably, the negative electrode material is described
Calcium containing compound, the particularly preferred negative electrode material are Ca2N。
According to the present invention, although to the source of the calcium containing compound, there is no particular limitation, in order to be conducive to obtain
Be more suitable for the electrode slice of sodium-ion battery, under preferable case, the preparation method of the calcium containing compound includes: in inertia
Under atmosphere or vacuum condition, the Ca that will be sealed in refractory metal vessel3N2Heated, the item of the heat treatment
Part includes: to be warming up to 800-1500 DEG C with the rate of heat addition of 1-20 DEG C/min, and keep the temperature 8-15h.
Wherein, for sealing Ca3N2Refractory metal vessel in addition to can be used as Ca3N2Container effect, constitute should
The refractory metal of container can also absorb the nitrogen that thermal decomposition generates, to help Ca3N2It is decomposed into Ca2N.The high-melting-point gold
Belong to container preferably by selected from one of tungsten, molybdenum, niobium, tantalum, vanadium, zirconium, rhenium and hafnium or a variety of formation, particularly preferably by selected from tungsten,
One of molybdenum, tantalum, vanadium, zirconium, rhenium and hafnium or a variety of formation, still more preferably for by tungsten, tantalum, vanadium, zirconium, rhenium and hafnium
One or more formation.The container for example can be the form of crucible.
Wherein, by Ca3N2The method for being sealed in the refractory metal vessel can adopt with the conventional methods in the field into
Row, such as can be in the glove box of inert atmosphere (such as by one of helium, argon gas and neon or a variety of offers), it will
Ca3N2Particulate abrasive is fitted into the refractory metal vessel at powder, is sealed by the way of thread seal.
Wherein, Ca will be sealed with3N2Refractory metal vessel be placed under inert atmosphere or vacuum condition, and carry out described in
Heat treatment can obtain Ca in high yield2N.Wherein, the condition of the heat treatment includes: the heating speed with 1-20 DEG C/min
Rate is warming up to 800-1500 DEG C, and keeps the temperature 8-15h.When the temperature of heat treatment is lower than 800 DEG C, it will product occur is Ca3N2
And Ca2The mixture of N；When the temperature of heat treatment is higher than 1500 DEG C, can not only there be higher energy consumption, but also one can be generated
A little impurity.
But in order to obtain more pure Ca2N, and not will lead to too big energy consumption, under preferable case, the heat treatment
Condition include: that 800- is warming up to the rate of heat addition of 5-15 DEG C/min (preferably 5-10 DEG C/min, more preferable 5-8 DEG C/min)
1500 DEG C (preferably 900-1400 DEG C, more preferably 1000-1300 DEG C are still more preferably 1100-1200 DEG C, most preferably
It is 1100-1150 DEG C), and keep the temperature 8-15h (preferably 9-15h, more preferably 10-15h are still more preferably 10-14h, most
Preferably 12-14h).
In a preferred embodiment of the invention, the condition of the heat treatment includes: with 5-15 DEG C/min
The rate of heat addition is warming up to 1100-1200 DEG C, and keeps the temperature 9-15h.
In a preferred embodiment of the invention, the condition of the heat treatment includes: with 5-10 DEG C/min
The rate of heat addition is warming up to 1100-1150 DEG C, and keeps the temperature 12-14h.
In a kind of more preferably embodiment of the invention, the condition of the heat treatment includes: with 5-6 DEG C/min
The rate of heat addition be warming up to 1100-1120 DEG C, and keep the temperature 12-13h.
Wherein, the above-mentioned rate of heat addition can be speed change, be also possible at the uniform velocity, just in the above range, excellent
It selects the rate of heat addition used for the rate of heat addition at the uniform velocity, the condition of heat treatment can be controlled more conveniently in this way.
Wherein, to the heating starting point of the heat treatment, there is no particular limitation, as long as not will lead to Ca3N2Start to decompose
, it is preferable that the heat treatment is started to warm up from 20-50 DEG C, is particularly preferably started to warm up from 20-40 DEG C.
Wherein, above-mentioned heat-treatment process can carry out in an inert atmosphere, can also carry out under vacuum conditions, this hair
Bright to this, there is no particular limitation, wherein the inert atmosphere for example can be by one of helium, argon gas and neon or a variety of
It provides.The vacuum condition for example can be gauge pressure -0.01MPa to -0.1MPa, preferably gauge pressure -0.05MPa to -0.1MPa.
Wherein, above-mentioned heat-treatment process can carry out in the various devices of this field routine, as long as can reach
Condition is stated, such as above-mentioned heat-treatment process can carry out in tube furnace.
Wherein, in order to after the heat treatment, needing that Ca will be sealed with3N2Refractory metal vessel be cooled to
Room temperature (such as 10-40 DEG C).The cooling rate can be 1-10 DEG C/min.
Wherein, the preparation method of above-mentioned calcium containing compound can not use Ca as reducing agent under, with higher yield
Ca is made2N, such as yield can reach 80% or more, preferably 90% or more；And resulting Ca2N is purer.Electrode slice of the invention
It is preferred that the resulting product of the preparation method of above-mentioned calcium containing compound is used without purifying directly as negative electrode material.Change sentence
It talks about, it can be understood as the negative electrode material is the resulting product without purifying of preparation method of above-mentioned calcium containing compound.
According to the present invention, the dosage of the negative electrode material can change in a wider range, it is preferable that with binder (with
Dry weight meter), on the basis of the total weight of conductive agent and negative electrode material, the content of the negative electrode material is 60-80 weight %.
According to the present invention, the sealant can be this field routine for sealing the sealing that collector prepares electrode slice
Layer, and those skilled in the art also it is clear that the sealant not only have the function of seal collector a face,
But also it is conductive.For this purpose, the sealant is made of binder and conductive agent, it is preferable that the binder and conduction
The weight ratio of agent is 1:1-3 (binder is in terms of dry weight).
Wherein, the binder is preferably one of Kynoar, polytetrafluoroethylene (PTFE) and polymethyl methacrylate
Or it is a variety of.Wherein, the conductive agent is preferably one of acetylene black, Super P, carbon nanotube and graphite or a variety of.
According to the present invention, the collector can use the various collectors of this field routine, but in order to enable afflux
The material of body can preferably be suitable for Ca2This negative electrode material of N, it is preferable that the collector is nickel foam, foam copper, bubble
One of foam titanium, foam iron-nickel, stainless (steel) wire and carbon cloth are a variety of.
The present invention also provides a kind of preparation methods of electrode slice, this method comprises:
(1) conductive agent and binder solution are mixed, sealing slurry is made；
(2) slurry will be sealed to be coated in the one side of collector, and dry, the afflux in one side with sealant is made
Body；
(3) negative electrode material will be inserted in the hole of step (2) resulting collector；
(4) collector obtained by pressing step (3)；
Wherein, the negative electrode material contains calcium containing compound, and the calcium containing compound of 50 weight % or more is Ca2N。
The negative electrode material is as introduced above, and details are not described herein.
According to the present invention, in step (1), the conductive agent and binder are as described above, and details are not described herein.
It wherein, for example can be N-methyl pyrrolidones, N-methyl formamide and tetrahydro furan as the solvent in the binder solution
It one of mutters or a variety of.The binder solution can be homemade, i.e., is dissolved into the polymer as binder centainly
Solvent in obtain.Preferably, the concentration of the binder solution is 1-8 weight %.
According to the present invention, as described above, it is preferable that the weight ratio of the binder and conductive agent is that 1:1-3 is (described
Binder is in terms of dry weight).
According to the present invention, step (2) is by the way that the resulting sealing slurry of step (1) to be coated in the one side of collector, so
After be dried, can be prepared by one side have sealant collector.Wherein, the collector is as described above,
This is repeated no more.The condition of the drying preferably includes: temperature is 50-100 DEG C, time 8-24h.It is highly preferred that described dry
Dry condition preferably includes: temperature is 80-100 DEG C, time 10-12h.
According to the present invention, negative electrode material is inserted to by the mode of the hole of step (2) resulting collector in step (3)
It can be carried out using any appropriate method, such as can the hereinbefore described hand for opening the refractory metal vessel
In casing, when taking out negative electrode material, is inserted into the hole of collector, i.e., negative electrode material is scattered in collector and be not coated with
The one side of sealant, so that the powder of negative electrode material enters in hole.Under preferable case, negative electrode material described in step (3)
Dosage makes, described on the basis of the total weight of binder (being counted by dry weight), conductive agent and negative electrode material in the electrode slice
The content of negative electrode material is 60-80 weight %.
According to the present invention, electrode slice can be obtained in collector compression moulding obtained by step (3) by step (4), for the ease of
Collector obtained by step (3) can first be fitted into after sealing in valve bag and suppress again by compacting.Under preferable case, step (4)
In, the condition of the compacting includes: that temperature is 10-40 DEG C, time 1-3min, pressure 5-10MPa.Pass through the side of compacting
Formula, so that avoiding the Ca to humidity sensitive2N is directly blended with binder, solves Ca2N and the incompatible problem of binder, again
Ca can be increased2The contact area of N and collector improve electronic conduction.
The present invention also provides electrode slices prepared by the above method.
The present invention also provides a kind of sodium-ion batteries, wherein the cathode of the sodium-ion battery is above-mentioned electrode slice.
According to the present invention, the sodium-ion battery can be full battery, may also mean that half-cell.Wherein, for testing
When the electrical property of electrode slice, then tested using half-cell.The half-cell can also include to electrode, diaphragm and electrolysis
Liquid.It wherein, is metallic sodium piece to electrode.Wherein, the effect of diaphragm be avoid positive and negative anodes from directly contacting to lead to battery short circuit, such as
It can be using the diaphragm of the Celgard2400 trade mark purchased from Whatman company.Wherein, the electrolyte can be NaPF6Or
NaClO4Ethylene carbonate and diethyl carbonate mixed solution, NaPF6Or NaClO4Concentration can be 1-2mol/L, carbon
The volume ratio of vinyl acetate and diethyl carbonate can be 1-2:1.
The sodium-ion battery can be assembled into the form of button cell in the glove box full of inert gas.
By using electrode slice of the invention, the sodium-ion battery of reversible discharge specific capacity can be obtained.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, the content of negative electrode material is by binder (in terms of dry weight), conduction in electrode slice
It is calculated on the basis of the total weight of agent and negative electrode material.
The dosage of following Kynoar binder refers to the dosage of the polymer of Kynoar, as binder
Dry weight.
Ca2The yield of N refers to the weight and Ca of actual production2The weight percent of the theoretical yield of N；Wherein actual production
For Ca3N2Powder weight after pyrolytic is cooled to room temperature, in crucible；Theoretical yield is according to decomposition equation: 4Ca3N2→
6Ca2N+N2, then 800mg Ca3N2Pyrolytic, theoretically calculating can get 762.2084mg Ca2N。
Preparation example 1
This preparation example is for illustrating Ca of the invention2The preparation method of N.
(1) in the glove box of argon gas protection, by the Ca of 800mg3N2It is added to tungsten crucible (purity 99.95%, purchased from treasured
Ji Chuanqi metal Co., Ltd Φ 20*5*40mm) in, it is sealed by the way of thread seal；
(2) tungsten crucible being sealed is taken out to tube furnace (the Sigma Corporation's SGM1001/A type for being placed in argon gas protection
Number, it is the same below) in, 1100 DEG C are warming up to the rate of heat addition of 5 DEG C/min since 25 DEG C, and calcining is kept the temperature at 1100 DEG C
12h；Room temperature (about 25 DEG C) are then cooled to the cooling rate of 5 DEG C/min；
Crucible is opened from glove box, obtains the powder 705mg of blackish green gloss, yield 92.5%, as cathode material
Expect that A1, the powder of the blackish green gloss are detected through X-ray diffractometer (with Ca undoped with red powder2The standard spectrum of N is compared
It is right) gained powder be Ca2N。
Preparation example 2
This preparation example is for illustrating Ca of the invention2The preparation method of N.
(1) in the glove box of argon gas protection, by the Ca of 800mg3N2It is added to zirconium crucible (purity 99.95%, purchased from treasured
Ji Chuanqi metal Co., Ltd Φ 20*5*40mm) in, it is sealed by the way of thread seal；
(2) zirconium crucible being sealed is taken out and is placed in the tube furnace of argon gas protection, with 8 DEG C/min's since 20 DEG C
The rate of heat addition is warming up to 1150 DEG C, and the heat preservation calcining 13h at 1150 DEG C；Room is then cooled to the cooling rate of 5 DEG C/min
Warm (about 25 DEG C)；
Crucible is opened from glove box, obtains the powder 668mg of blackish green gloss, yield 87.6%, as cathode material
Expect that A2, the powder of the blackish green gloss are detected through X-ray diffractometer (with Ca undoped with red powder2The standard spectrum of N is compared
It is right) gained powder be Ca2N。
Preparation example 3
This preparation example is for illustrating Ca of the invention2The preparation method of N.
According to the method for preparation example 1, unlike, the rate of heat addition heating in step (2) with 15 DEG C/min replace 5 DEG C/
The rate of heat addition of min；It is final to open crucible, obtain partially dimmed powder 617mg, yield 80.9%, as negative electrode material
A3, the partially dimmed powder are since the powder of blackish green gloss is caused doped with very small amount of red powder, through X-ray
Diffractometer detects (with Ca2The standard spectrum of N is compared) gained powder be Ca2N, and have faint Ca3N2Signal.
Preparation example 4
This preparation example is for illustrating Ca of the invention2The preparation method of N.
According to the method for preparation example 1, the difference is that, heat preservation calcining 12h at 1000 DEG C is warming up in step (2)；Finally beat
Open crucible, obtain dimmed powder 721mg, yield 94.6%, as negative electrode material A4, the dimmed powder be due to
The powder of blackish green gloss is caused doped with a small amount of red powder, is detected through X-ray diffractometer (with Ca2The standard spectrum of N carries out
Compare) gained powder be Ca2N and a small amount of Ca3N2Mixture.
Preparation example 5
According to the method for preparation example 1, unlike, the rate of heat addition heating in step (2) with 30 DEG C/min replace 5 DEG C/
The rate of heat addition of min；It is final to open crucible, the powder 577mg of black is obtained, yield 75.7%, as negative electrode material A5 should
The powder of black is to detect since the powder of blackish green gloss is caused doped with larger amount of red powder through X-ray diffractometer
(with Ca2The standard spectrum of N is compared) gained powder be Ca2N and a small amount of Ca3N2Mixture, and have less impurity signal.
Embodiment 1
The present embodiment is for illustrating electrode slice and preparation method thereof of the invention.
(1) the conductive agent Super P of 20mg (being purchased from TIMICAL company, the same below) and the Kynoar of 10mg is (poly-
Vinylidene ships the U.S. Su Wei 1015 of plastic material company purchased from Dongguan City gold, which is formulated as by when use
The solution (solvent is that N-methyl pyrrolidones is purchased from Sinopharm Chemical Reagent Co., Ltd.) of 5 weight %) ground and mixed is carried out,
Sealing slurry is made；The sealing slurry is coated in nickel foam (purchased from Shenzhen's benefit Fetion environmental protection equipment Co., Ltd, the same below)
One side on, and be dried in vacuo 12h at 80 DEG C, there is the nickel foam of sealant to be cut to the disk of diameter 10mm gained；
(2) in the glove box of argon gas protection, 70mg negative electrode material A1 is sprinkling upon to the one of the nickel foam for being not coated with sealant
Face, and the pico- shaking in left and right, so that the hole of negative electrode material A1 filling nickel foam；After being sealed with valve bag, taken from glove box
Out, and under room temperature (about 25 DEG C) 1min is suppressed with 8Mpa pressure, is transferred in glove box, is taken out from valve bag, obtains electricity
Pole piece P1, wherein the content of negative electrode material is 70 weight %.
Embodiment 2
The present embodiment is for illustrating electrode slice and preparation method thereof of the invention.
(1) Kynoar of conductive agent the Super P and 10mg of 10mg are subjected to ground and mixed, sealing slurry is made；
The sealing slurry is coated in the one side of nickel foam, and is dried in vacuo 12h at 100 DEG C, gained is had to the foam of sealant
Nickel is cut to the disk of diameter 10mm；
(2) in the glove box of argon gas protection, 80mg negative electrode material A2 is sprinkling upon to the one of the nickel foam for being not coated with sealant
Face, and the pico- shaking in left and right, so that the hole of negative electrode material A2 filling nickel foam；After being sealed with valve bag, taken from glove box
Out, and under room temperature (about 25 DEG C) 1min is suppressed with 8Mpa pressure, is transferred in glove box, is taken out from valve bag, obtains electricity
Pole piece P2, wherein the content of negative electrode material is 80 weight %.
Embodiment 3
The present embodiment is for illustrating electrode slice and preparation method thereof of the invention.
(1) Kynoar of the conductive agent acetylene black of 30mg and 10mg are subjected to ground and mixed, sealing slurry is made；It will
The sealing slurry is coated in the one side of nickel foam, and is dried in vacuo 12h at 80 DEG C, there is the nickel foam of sealant to cut out gained
It is cut to the disk of diameter 10mm；
(2) in the glove box of argon gas protection, 60mg negative electrode material A1 is sprinkling upon to the one of the nickel foam for being not coated with sealant
Face, and the pico- shaking in left and right, so that the hole of negative electrode material A1 filling nickel foam；After being sealed with valve bag, taken from glove box
Out, and under room temperature (about 25 DEG C) 1min is suppressed with 8Mpa pressure, is transferred in glove box, is taken out from valve bag, obtains electricity
Pole piece P3, wherein the content of negative electrode material is 60 weight %.
Embodiment 4
According to method described in embodiment 1, the difference is that, A1 is replaced using negative electrode material A3；Electrode slice P4 is obtained,
In, the content of negative electrode material is 70 weight %.
Embodiment 5
According to method described in embodiment 1, the difference is that, A1 is replaced using negative electrode material A4；Electrode slice P5 is obtained,
In, the content of negative electrode material is 70 weight %.
Embodiment 6
According to method described in embodiment 1, the difference is that, A1 is replaced using negative electrode material A5；Electrode slice P6 is obtained,
In, the content of negative electrode material is 70 weight %.
Comparative example 1
According to method described in embodiment 1, the difference is that, it uses weight ratio as the Ca of 1:13N2Make with negative electrode material A1
It is negative electrode material to replace individually by negative electrode material A1 as negative electrode material；To obtain electrode slice DP1, wherein negative electrode material
Content be 70 weight %.
Comparative example 2
According to method described in embodiment 1, the difference is that, using Ca3N2As negative electrode material to replace negative electrode material A1；
To obtain electrode slice DP2, wherein the content of negative electrode material is 70 weight %.
Battery testing example
Respectively using electrode slice obtained as above as working electrode, using metallic sodium piece as to electrode, Celgard2400
(being purchased from Whatman company) makees diaphragm, the NaClO of electrolyte 1mol/L4Ethylene carbonate (EC) and diethyl carbonate
(DEC) mixed solution (volume ratio of EC:DEC is 1:1), wherein be assembled into experiment knob in the glove box full of argon atmosphere
Battery is detained, is 130mA/cm in constant current density after standing for 24 hours on LAND CT2001A tester2The electric circulation of lower progress
Test, the results are shown in Table 1.
Table 1: the electrical property of gained battery under Different electrodes piece
It can be seen from Table 1 that using Ca in P1-P62N is as negative electrode material, for Shi Keshi in sodium-ion battery
The existing reversible charge and discharge of height ratio capacity.Wherein, the negative electrode material Ca of electrode slice P1-P42N crystal form development is more complete, is more advantageous to
The abjection and insertion of sodium ion.It can be seen that by comparative example, be mixed with Ca3N2Electrode slice, chemical property be not very well, this can
Energy and Ca3N2、Ca2Conductivity difference between N is related, Ca2N has characteristic of semiconductor, electric conductivity ratio as electrification daughter
Ca3N2It gets well, no doubt chemical property ratio Ca3N2It is high.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of electrode slice, which is characterized in that this method comprises:
(1) conductive agent and binder solution are mixed, sealing slurry is made；
(2) slurry will be sealed to be coated in the one side of collector, and dry, the collector that one side has sealant is made；
(3) negative electrode material will be inserted in the hole of step (2) resulting collector；
(4) collector obtained by pressing step (3)；
Wherein, the negative electrode material contains calcium containing compound, and the calcium containing compound of 50 weight % or more is Ca2N,
This method further includes the steps that preparing the calcium containing compound using following steps: under inert atmosphere or vacuum condition,
The Ca that will be sealed in refractory metal vessel3N2Heated, the condition of the heat treatment include: with 5-10 DEG C/
The rate of heat addition of min is warming up to 1100-1150 DEG C, and keeps the temperature 12-14h, and the refractory metal vessel is by tungsten, zirconium
One or two kinds of formed.
2. according to the method described in claim 1, wherein, in the negative electrode material, the calcic chemical combination of 80 weight % or more
Object is Ca2N。
3. according to the method described in claim 2, wherein, in the negative electrode material, the calcic chemical combination of 90 weight % or more
Object is Ca2N。
4. according to the method described in claim 1, wherein, in step (1), the binder is Kynoar, polytetrafluoroethyl-ne
One of alkene and polymethyl methacrylate are a variety of；The conductive agent is acetylene black, Super P, carbon nanotube and graphite
One of alkene is a variety of.
5. method according to claim 1 or 4, wherein the weight ratio of the binder and conductive agent is 1:1-3.
6. method described in any one of -4 according to claim 1, wherein the dosage of negative electrode material described in step (3) makes
, in the electrode slice, on the basis of the total weight of binder, conductive agent and negative electrode material, the content of the negative electrode material is
60-80 weight %.
7. according to the method described in claim 1, wherein, the collector be nickel foam, foam copper, titanium foam, foam iron-nickel,
One of stainless (steel) wire and carbon cloth are a variety of.
8. according to the method described in claim 1, wherein, in step (4), the condition of the compacting includes: that temperature is 10-40
DEG C, time 1-3min, pressure 5-10MPa.
9. electrode slice made from a kind of method as described in any one of claim 1-8.
10. a kind of sodium-ion battery, wherein the cathode of the sodium-ion battery is electrode slice as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610329954.6A CN106058149B (en) | 2016-05-18 | 2016-05-18 | Electrode slice and preparation method thereof and sodium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610329954.6A CN106058149B (en) | 2016-05-18 | 2016-05-18 | Electrode slice and preparation method thereof and sodium-ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106058149A CN106058149A (en) | 2016-10-26 |
| CN106058149B true CN106058149B (en) | 2019-06-04 |
Family
ID=57177365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610329954.6A Active CN106058149B (en) | 2016-05-18 | 2016-05-18 | Electrode slice and preparation method thereof and sodium-ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106058149B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109959869B (en) * | 2017-12-21 | 2021-11-09 | 中南大学 | Lithium-empty buckle type battery testing device |
| CN109959868B (en) * | 2017-12-21 | 2021-12-10 | 中南大学 | Novel lithium-oxygen button cell test bottle |
| CN117219851B (en) * | 2023-11-09 | 2024-03-15 | 宁德时代新能源科技股份有限公司 | Sodium secondary battery and electricity utilization device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007207663A (en) * | 2006-02-03 | 2007-08-16 | Matsushita Electric Ind Co Ltd | Method of manufacturing negative electrode of lithium-ion secondary battery, and lithium-ion secondary battery including negative electrode obtained using its method |
| CN102082267A (en) * | 2011-01-06 | 2011-06-01 | 浙江大学 | Preparation and application of conductive carbon film-coated calcium nitride compound serving as anode material of lithium battery |
| CN102437313A (en) * | 2011-12-08 | 2012-05-02 | 中国电子科技集团公司第十八研究所 | Negative electrode for high-power metal lithium battery |
| CN105098142A (en) * | 2014-05-06 | 2015-11-25 | 深圳市沃特玛电池有限公司 | Coating method for lithium-ion battery pole piece |
-
2016
- 2016-05-18 CN CN201610329954.6A patent/CN106058149B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007207663A (en) * | 2006-02-03 | 2007-08-16 | Matsushita Electric Ind Co Ltd | Method of manufacturing negative electrode of lithium-ion secondary battery, and lithium-ion secondary battery including negative electrode obtained using its method |
| CN102082267A (en) * | 2011-01-06 | 2011-06-01 | 浙江大学 | Preparation and application of conductive carbon film-coated calcium nitride compound serving as anode material of lithium battery |
| CN102437313A (en) * | 2011-12-08 | 2012-05-02 | 中国电子科技集团公司第十八研究所 | Negative electrode for high-power metal lithium battery |
| CN105098142A (en) * | 2014-05-06 | 2015-11-25 | 深圳市沃特玛电池有限公司 | Coating method for lithium-ion battery pole piece |
Non-Patent Citations (2)
| Title |
|---|
| 2D Electrides as Promising Anode Materials for Na-Ion Batteries from First-Principles Study;Junping Hu，Bo Xu，Shengyuan A. Yang等;《Acs Applied Materials & Interfaces》;20151013;第7卷(第43期);参见摘要 |
| Dicalcium nitride, Ca2N—a 2D "excess electron compound"；synthetic routes and crystal chemistry;Duncan H.Gregory，Amy Bowman等;《Journal of Materials Chemistry》;20000621;第10卷(第7期);参见Experimental |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106058149A (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105789584B (en) | A kind of cobaltous selenide/carbon sodium-ion battery composite negative pole material and the preparation method and application thereof | |
| CN105914374B (en) | Composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application | |
| CN108394884A (en) | A kind of preparation method of chitosan-based high-specific surface area nitrogen/phosphor codoping carbon nanosheet | |
| CN106505185B (en) | A kind of antimony/nitrogen-doped carbon compound and its preparation method and application | |
| CN108059144B (en) | Hard carbon prepared from biomass waste bagasse, and preparation method and application thereof | |
| CN106920989B (en) | A kind of copper selenium compound is the sodium-ion battery of negative electrode material | |
| CN108767260A (en) | A kind of hollow nano-electrode materials of carbon coating FeP and its preparation method and application | |
| CN106744798B (en) | A kind of method and its application preparing hard carbon using carbon containing biological mass shell | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| CN107768645B (en) | Porous nitrogen-doped carbon nanosheet composite negative electrode material and preparation method thereof | |
| CN105161692A (en) | Preparation method for C-MoS2 composite material and products and electrochemical application thereof | |
| Wen et al. | Electrochemical performances of ZnO with different morphology as anodic materials for Ni/Zn secondary batteries | |
| CN107180964A (en) | A kind of microwave method prepares method and the application of blended metal oxide/graphene composite nano material | |
| CN107248569A (en) | Using the methylimidazole cdicynanmide of 1 ethyl 3 antimony made from carbon source/nitrogen-doped carbon compound and its preparation method and application | |
| CN109659540A (en) | A kind of preparation method of porous carbon coating antimony telluride nanometer sheet and its application as metal ion cell negative electrode material | |
| CN105118966B (en) | A kind of high nitrogen-containing tin carbon composite for cathode of lithium battery and preparation method | |
| CN109461916A (en) | A kind of preparation method of anode material of lithium-ion battery | |
| CN108933047A (en) | A kind of prelithiation gel electrolyte and preparation method thereof for lithium-ion capacitor | |
| CN106229503A (en) | The preparation method of a kind of nickel oxide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery | |
| CN106058149B (en) | Electrode slice and preparation method thereof and sodium-ion battery | |
| CN105719846B (en) | A kind of preparation method of cobalt sulfide/carbon composite and products thereof and application | |
| CN106058213B (en) | A kind of two stannic selenides/polyethyleneimine composite material and its preparation method and application | |
| CN105680050B (en) | A kind of cell negative electrode material of 2-methylimidazole zinc salt pyrolysis gained | |
| CN108807911A (en) | A kind of aluminium ion battery and preparation method thereof | |
| CN109928384A (en) | A kind of preparation method of nitrogen-doped porous carbon material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |