CN110289406A - A kind of three-dimensional crosslinking structure combination electrode material and the preparation method and application thereof - Google Patents
A kind of three-dimensional crosslinking structure combination electrode material and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to electrochemical fields, and in particular to a kind of three-dimensional crosslinking structure combination electrode material and the preparation method and application thereof.The combination electrode material includes: to be made of multiple unitary spaces, and the unitary space is cross-linked to form by adjacent sheets, and the lamella is formed by two-dimentional transition metal carbide or carbonitride；Amorphous carbon disperses and is supported in the unitary space；Nano silicon particles are wrapped in the unitary space.The combination electrode material can be used as lithium ion battery negative material, make it have the advantages that specific discharge capacity is high, cyclicity is good, long service life and power are high.
Description
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of three-dimensional crosslinking structure combination electrode material and preparation method thereof
With application.
Background technique
Energy density is big, average output voltage is high, self discharge is low, memory-less effect, uses the longevity because having for lithium ion battery
Life is long, comparatively safe cost is relatively low, cycle performance works fine voltage range is big, without memory effect, cycle life number it is high,
The advantages that environmentally protective, is widely used in various portable energy-storing devices and equipment.The performance of lithium ion battery depends primarily on
Positive and negative pole material, and the negative electrode material for developing higher energy density is current one of research emphasis.
The negative electrode material of lithium ion battery is divided into carbon based negative electrodes material and non-carbon negative electrode material.Carbon-based material is current master
The lithium ion battery negative material of stream, wherein graphite is most widely used.The graphite reason welcome as negative electrode material be,
Due to its layer structure, there is stable capacity in repetitive cycling, invertibity is quite high.However, Carbon anode theoretical capacity is only
There are 372mAh/g and typical non-renewable resources, and its exploitation and process easily bring serious pollution.Therefore, it opens
The high capacity cathode for sending out new is very necessary.
In non-carbon negative material, silicon due to its higher theoretical specific capacity (4200mAh/g) and discharge potential it is low, from
The advantages such as right rich reserves, become the most potential lithium ion battery negative material of substitution graphite.However, silicon materials lithium from
During son insertion and abjection, up to 300% volume change is had, this will lead to electrode structure and destroys, be electrically connected failure, be living
Property material the problems such as persistently consuming, eventually leading to battery capacity decays rapidly, and cycle performance deteriorates.
Currently, the main method for improving silicium cathode is by silicon materials nanosizing, such as nano thin-film, nano wire, nano particle
Deng.The silicon of nanosizing can preferably discharge the stress of volume change generation, while provide the space of volume expansion.However due to
The intrinsic conductivity of silicon is low, and the silicon of nanosizing still suffers from obvious capacity attenuation over numerous cycles, and the power of battery is close
It spends relatively low.M.Holzapfel, N.Liu etc. are not only conducive to the electronic conduction of reinforcing material using the composite material of silicon and carbon
Property, while the light weight of carbon material, ductile characteristic are also beneficial to stress release.But traditional carbon material is in silicon cycling mistake
Cheng Zhong, it is easy to break, cause the capacity attenuation after more cycle-index to become faster, and unbodied carbon material limits electronics biography
Lead rate.
Two-dimentional transition metal carbide or carbonitride (abbreviation MXenes) are by Univ Drexel, the U.S. (Drexel
University the one kind of Yury Gogotsi professor and Michel W.Barsoum professor) et al. in cooperation discovery in 2011
New Two Dimensional structural material.Since self-discovery, two-dimentional transition metal carbide or carbonitride series are rapidly developed.It is so far
Only, about 20 kinds of different MXenes have been synthesized, and have theoretically predicted tens of kinds of different structures and property.
MXenes chemical general formula can use Mn+1XnTxIt indicates, wherein M refers to magnesium-yttrium-transition metal (such as Ti, Zr, Hf, V, Nb, Ta, Cr, Sc), X
Refer to that carbon C or/and nitrogen N, n are generally 1-3, Tx refers to surface group (such as O2-、OH-、F-、NH3、NH4 +Deng).MXenes has Gao Bibiao
The characteristics of area, high conductivity, strongly hydrophilic, flexibly adjustable but also with component, the advantages such as minimum nanometer thickness is controllable are being stored up
Can, absorption, electromagnetic interference shield, composite material enhancing, Water warfare, gas and biosensor, lubrication, photoelectricity, electrochemistry and
The fields such as chemical catalysis show huge potentiality.
Currently, existing research show two-dimentional transition metal carbide or carbonitride can be used for secondary cell anode or
Negative electrode material, as CN109449404A discloses a kind of lithium sulfur battery anode material sulphur-nitrogen-doped carbon nano-fiber-MXene
Composite material and preparation method；CN108155409A discloses a kind of barium base Dual-ion cell and preparation method thereof, wherein barium
Base Dual-ion cell includes cathode, anode, diaphragm and electrolyte between positive and negative anodes；Negative electrode material active material is energy
It is enough reversibly embedded in, the stratified material of deintercalation barium ions；Stratified material includes graphite carbon material, Prussian blue and its similar
In object, sulfide, tunnel structure Mn oxide, metal-organic framework materials, two-dimentional transition metal carbide or carbonitride
One kind or at least two.However, at present in field of batteries also only with the chemical property of Mxene, to its other function
It needs further to develop.
Summary of the invention
In order to solve lithium ion battery silicon cathode material because of battery existing for silicon particle volume change is larger, conductivity is lower
Capacity attenuation is very fast, and cycle performance is bad, and service life is shorter, the lower problem of cell power density, and the present invention is special to propose one
Kind three-dimensional crosslinking structure combination electrode material.The combination electrode material can be used as lithium ion battery negative material, make it have
The advantages that specific discharge capacity is high, cyclicity is good, long service life and power are high.
Combination electrode material of the present invention, comprising:
Three-dimensional cross-linked frame is made of multiple unitary spaces；The unitary space is cross-linked to form by adjacent sheets；Described
Layer is formed by two-dimentional transition metal carbide or carbonitride (MXenes)；
Amorphous carbon (Disorder Carbon) disperses and is supported in the unitary space；
Nano silicon particles (SiNPs), are wrapped in the unitary space.
The present invention introduces MXene in existing silicon nanometer anode material, forms three-dimensional cross-linked frame by it, is silicon nanometer
The volume expansion of grain provides a large amount of expansion space.
More importantly the present invention also introduces PVA, expansion space is provided for nano silicon particles by being pyrolyzed, and it is hot
The amorphous carbon that solution is formed provides support in three-dimensional cross-linked frame, is conducive to the structural integrity for keeping negative electrode active material；Together
When, even if silicon can still result in the broken of structure during expansion and contraction, but breaked nano silicon particles are still protected
It stays in unitary space, it is difficult to which abjection and electrolyte solution contacts reduce the generation of irreversible capacity in cyclic process.
Moreover, amorphous carbon also forms conductive network with MXene, solves the intrinsic electricity of silicon on vertical slice in-plane
The low problem of conductance, the transmission for electronics during charging, discharging electric batteries provide channel, are conducive to the transmission road for shortening electronics
Diameter；Meanwhile Li+It can be carried out via the defect of MXene sheet surfaces quickly " insertion " and " deintercalation ".In short, institute of the present invention
The combination electrode material stated is used for the cathode of lithium ion battery, may make battery to have capacity high and is not easy to decay, and cyclicity is good,
The advantages that long service life.
According to an embodiment of the invention, the chemical general formula of the two dimension transition metal carbide or carbonitride can use Mn+ 1XnTxIt indicates, wherein M refers to magnesium-yttrium-transition metal, such as Ti, Zr, Hf, V, Nb, Ta, Cr, Sc, and X refers to that carbon C or/and nitrogen N, n are generally
1-3, Tx refer to surface group, such as O2-、OH-、F-、NH3、NH4 +Deng；Preferably, the two-dimentional transition metal carbide or carbon nitridation
Object is selected from Ti3C2Tx、Ti2CTx、Zr2C Tx、Hf2CTx、Sc2One of CTx or a variety of；Wherein Tx is surface group O2-、
OH-、F-、NH3、NH4 +。
According to an embodiment of the invention, the diameter of the lamella is 500-1000nm, the partial size of nano silicon particles is 30-
50nm。
It is described two dimension transition metal carbide or carbonitride, nano silicon particles, amorphous carbon mass ratio be (1-2):
(4-1): (1-2), preferably 1:1:1.
According to an embodiment of the invention, the amorphous carbon is pyrolyzed by polyvinyl alcohol (polyvinyl alcohol, PVA)
It obtains, for nano silicon particles, cubic deformation during charging, discharging electric batteries provides pre- leave a blank in the gap that pyrolytic process is formed
Between.
The present invention also provides a kind of preparation methods of above-mentioned combination electrode material, comprising:
(1) by etching presoma, the aqueous solution of two-dimentional transition metal carbide or carbonitride is prepared；
(2) nano silicon particles and PVA are mixed, ball milling is added to the water of two-dimentional transition metal carbide or carbonitride
In solution, dispersion, ultrasound obtains mixed liquor；
(3) mixed liquor is filtered using vacuum filtration method, obtains three-dimensional cross-linked composite material, pyrolysis processing is cooled to
Room temperature obtains combination electrode material.
The present invention is mixed using PVA with nano silicon particles, so that PVA is wrapped in nano silicon particles surface by ball milling；Package
The nano silicon particles of PVA are mixed with the aqueous solution of lamella two dimension transition metal carbide, while lamella is cross-linked to form reticular structure,
Using vacuum filtration mode, lamella is stacked together, forms closed edge, avoids electrolyte solution and penetrates into turn from edge
It is contacted with silicon；Again by pyrolysis processing, so that PVA is converted into amorphous carbon and be used to support the frame that two-dimentional transition metal carbide is formed
Frame structure, while space interval is formd in pyrolytic process, which is nano silicon particles during charging, discharging electric batteries
Volume expansion provides reserved space, is more advantageous to the structural intergrity for keeping electrode material, so that battery has capacity
It is high and be not easy to decay, the characteristics of cyclicity is good, long service life.Meanwhile the conductive network that MXeney and amorphous carbon are formed connects
Two-dimentional transition metal carbide (MXene) lamella is connect, the conductive network is during charging, discharging electric batteries, the transmission of electronics is mentioned
Channel has been supplied, the transmission path for shortening electronics is conducive to, thus, the charge-discharge velocity of battery is fast, and power-performance is good.Institute of the present invention
The preparation method stated has the advantages that easy to operate, preparation process easily realizes, raw material is easy to get.
According to an embodiment of the invention, it is described two dimension transition metal carbide or carbonitride MXene aqueous solution be by
Following method preparation: lithium fluoride (LiF) powder is dissolved in hydrochloric acid (HCl) solution, Ti is then gradually added into3AlC2, in 35 DEG C
Reaction 24 hours.Washing to pH value of solution is greater than 6；Acquired solution is diluted 50 times, is then ultrasonically treated 1 hour.
As one of preferred embodiment, the aqueous solution of the two dimension transition metal carbide MXene is by the following method
Preparation: lithium fluoride (LiF) powder of 1g is dissolved completely in 9M hydrochloric acid (HCl) solution of 20mL, is then gradually added into 1g's
Ti3AlC2In, solution is reacted 24 hours at 35 DEG C, removes Al layers.And with deionized water be centrifuged 5 minutes wash, circulation until
PH value of solution reaches greater than 6.Acquired solution is diluted 50 times, is then ultrasonically treated 1 hour.
According to an embodiment of the invention, the mass ratio of the nano silicon particles and PVA are 4:1~1:1, excellent in step (2)
Select 1:1.
According to an embodiment of the invention, in step (2), the condition of the ball milling are as follows: ratio of grinding media to material is (2-5): 1, preferably 3:
1.In order to ensure the crushing of amorphous carbon more evenly, ball milling steel ball should select it is small, in, big three kinds of various sizes of steel balls make jointly
For abrasive body, then ball grinder is put into planetary ball mill and is fixed by mass ratio 3:3:4.In order to ensure ball milling effect,
Material is avoided to be compacted in ball milling pot sidewall, setting rotational speed of ball-mill is 300r/min, each Ball-milling Time 60min, twice ball milling
Interval time be 5min, altogether circulation carry out 10 times.
According to an embodiment of the invention, the vacuum filtration method is to be filtered mixed liquor to filter membrane using vacuum filtration equipment
On, to form three-dimensional cross-linked composite construction；In order to obtain ideal three-dimensional structure, the operating condition of the vacuum filtration method
Are as follows: use water system micropore filtering film, diameter 50nm, aperture 0.45um.5min is filtered, is put into 35 DEG C of drying in baking oven after the completion
24h。
According to an embodiment of the invention, the operating condition of the ultrasound are as follows: frequency 10-20kHz, power 100-120W, when
Between 1-2h.
According to an embodiment of the invention, in step (3), the condition of the pyrolysis processing are as follows: under argon gas stream, pyrolysis temperature
It is 500-700 DEG C, preferably 600 DEG C；The rate of heat addition of the pyrolysis controls the preferably 5 DEG C/min between 5-10 DEG C/min.Stream
Dynamic 2h, and be cooled to room temperature with Temperature fall rate, obtain the combination electrode material of three-dimensional crosslinking structure.
The present invention also provides a kind of negative electrode of lithium ion battery comprising above-mentioned combination electrode material.Using above-mentioned compound
The cathode that electrode material is prepared has many advantages, such as that specific discharge capacity is high, cyclicity is good, long service life and power are high.
The present invention also provides a kind of lithium ion batteries comprising above-mentioned negative electrode of lithium ion battery.Using cathode of the invention
Lithium ion battery, battery capacity is high and is not easy to decay, and cyclicity is good, long service life, has good high rate performance ability.
According to an embodiment of the invention, lithium ion battery of the invention remains to maintain after 50 circulations the specific volume of 564.82mAh g-1
Amount, illustrates good cycle performance.
Detailed description of the invention
The preparation technology flow chart of Fig. 1 three-dimensional crosslinking structure combination electrode material of the present invention.
The charge and discharge electrical schematic of Fig. 2 three-dimensional crosslinking structure combination electrode of the present invention.
The SEM of Fig. 3 three-dimensional crosslinking structure combination electrode material of the present invention schemes.
The cycle performance curve graph of Fig. 4 three-dimensional crosslinking structure combination electrode material of the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, and for explaining only the invention, and is not considered as limiting the invention.
In the description of the present invention, term " longitudinal direction ", " transverse direction ", "upper", "lower", "front", "rear", "left", "right", " perpendicular
Directly ", the orientation or positional relationship of the instructions such as "horizontal", "top", "bottom" is to be based on the orientation or positional relationship shown in the drawings, and is only
For ease of description the present invention rather than require the present invention that must be constructed and operated in a specific orientation, therefore should not be understood as pair
Limitation of the invention.The present invention has designed and Implemented silicon/gap/carbon nano composite structure cathode lithium ion battery.
Embodiment 1
The present embodiment provides a kind of preparation methods of the combination electrode material of three-dimensional crosslinking structure, comprising:
(1) pass through etching presoma Ti3AlC2, prepare the aqueous solution of two-dimentional transition metal carbide MXene: by the fluorine of 1g
Change lithium (LiF) powder to be dissolved completely in 9M hydrochloric acid (HCl) solution of 20mL, then be gradually added into the Ti3AlC2 of 1g, it will be molten
Liquid reacts 24 hours at 35 DEG C, removes Al layers.And be centrifuged 5 minutes and washed with deionized water, circulation is until pH value of solution reaches big
In 6.Acquired solution is diluted 50 times, is then ultrasonically treated 1 hour.
(2) by nano silicon particles and PVA according to the quality of 1:1 than ball milling 1 hour after, two-dimentional transition metal carbide is added
(MXene) in aqueous solution, dispersed, to obtain the aqueous dispersion liquid of the two；
(3) the aqueous dispersion liquid is subjected to ultrasonic mixing, obtains mixed liquor；
(4) using vacuum filtration equipment, mixed liquor is filtered onto filter membrane, to form three-dimensional cross-linked composite construction；
(5) composite material is subjected to pyrolysis processing, is heated to 600 under argon gas stream with the rate of heat addition of 5 DEG C/min
DEG C, two hours are pyrolyzed, and be cooled to room temperature with natural rate, convert amorphous carbon for PVA, it is living to obtain the cathode
Property material.
Fig. 1 show the preparation technology flow chart of netted cladding structure electrode material, it is seen that MXene constitutes three-dimensional cross-linked
Frame structure, and amorphous carbon two-dimentional transition metal carbide interlayer provide support, provide sky for nano silicon particles
Between be spaced, the space be charging, discharging electric batteries during, silicon volume expansion provides reserved space, be conducive to keep negative electrode active
The structural integrity of material, so that the capacity of battery is high and is not easy to decay, cyclicity is good, long service life.
With the processing system of the netted cladding structure composite electrode material cathode of vacuum filtration method preparation vacuum filtration shown in Fig. 2
Make process, as shown in Figure 2, PVA coats nano silicon particles, with few layer of Ti3C2Tx ultrasonic mixing is filtered, and carbonization obtains compound
Material.
Fig. 3 show the SEM figure of resulting netted cladding structure composite electrode material after above-mentioned process flow, can see
Out, silicon particle is dispersed in two-dimentional transition metal carbide (MXene) interlayer, provides space for the expansion of silicon particle.Two dimension
The high conductivity of transition metal carbide (MXene) layer and amorphous carbon provides channel for the transmission of lithium ion and electronics.Wherein,
Fig. 3 a is the SEM figure of material before PVA pyrolysis is carbonized, and Fig. 3 b is the SEM figure of material after PVA pyrolysis carbonization, it is seen that is formed after pyrolysis
The expansion space of nano silicon particles.
In order to carry out electro-chemical test, button-shaped half-cell is made, test result is as follows:
Fig. 4 show the battery specific capacity during charge and discharge cycles.As shown, SiNPs/DC/Mxenes three-dimensional is handed over
Connection composite negative pole remains to maintain 564.82mAh g after 50 circulations-1Specific capacity, illustrate good cycle performance.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of combination electrode material characterized by comprising
It is made of multiple unitary spaces, the unitary space is cross-linked to form by adjacent sheets, and the lamella is by two-dimentional transition metal
Carbide or carbonitride are formed；
Amorphous carbon disperses and is supported in the unitary space；
Nano silicon particles are wrapped in the unitary space.
2. combination electrode material according to claim 1, which is characterized in that the two dimension transition metal carbide or carbon nitrogen
Compound is selected from Ti3C2Tx、Ti2CTx、Zr2C Tx、Hf2CTx、Sc2One of CTx or a variety of；Wherein Tx is surface group O2-、
OH-、F-、NH3、NH4 +。
3. combination electrode material according to claim 1 or 2, which is characterized in that the diameter of the lamella is 500-
1000nm, the partial size of nano silicon particles are 30-50nm.
4. combination electrode material according to claim 1 to 3, which is characterized in that the two dimension transition metal carbide
Or the mass ratio of carbonitride, nano silicon particles, amorphous carbon is (1-2): (4-1): (1-2), preferably 1:1:1.
5. combination electrode material according to claim 1 to 4, which is characterized in that the amorphous carbon is by polyvinyl alcohol
What pyrolysis obtained.
6. a kind of preparation method of any combination electrode material of claim 1-5, comprising:
(1) by etching presoma, the aqueous solution of two-dimentional transition metal carbide or carbonitride is prepared；
(2) nano silicon particles and PVA are mixed, ball milling is added to the aqueous solution of two-dimentional transition metal carbide or carbonitride
In, dispersion, ultrasound obtains mixed liquor；
(3) mixed liquor being filtered using vacuum filtration method, obtains three-dimensional cross-linked composite material, pyrolysis processing is cooled to room temperature,
Obtain combination electrode material.
7. preparation method according to claim 6, which is characterized in that in step (2), the nano silicon particles and PVA's
Mass ratio is 4:1~1:1, preferably 1:1；
And/or the condition of the ball milling are as follows: ratio of grinding media to material is (2-5): 1, preferably 3:1.
8. according to any preparation method of claim 6-7, which is characterized in that the vacuum filtration method uses water system micropore
Filter membrane；
And/or the operating condition of the ultrasound are as follows: frequency 10-20kHz, power 100-120W, time 1-2h；
And/or the condition of the pyrolysis processing are as follows: under argon gas stream, pyrolysis temperature is 500-700 DEG C, preferably 600 DEG C；
And/or the rate of heat addition of the pyrolysis controls the preferably 5 DEG C/min between 5-10 DEG C/min.
9. a kind of negative electrode of lithium ion battery, which is characterized in that including any combination electrode material of claim 1-5.
10. a kind of lithium ion battery, which is characterized in that including negative electrode of lithium ion battery as claimed in claim 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384381A (en) * | 2020-03-23 | 2020-07-07 | 北京化工大学 | Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof |
| CN112886019A (en) * | 2021-02-03 | 2021-06-01 | 山东大学 | High-stability three-dimensional MXene-COF-Li composite metal lithium negative electrode material and preparation method and application thereof |
| CN114242463A (en) * | 2021-11-19 | 2022-03-25 | 清华大学 | Anode active material, on-chip micro lithium ion capacitor comprising same and manufacturing method thereof |
| CN117362037A (en) * | 2023-10-16 | 2024-01-09 | 潍坊卓宇新材料科技有限公司 | Cadmium sulfide target piece processing technology and split processing die |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362311A (en) * | 2014-09-23 | 2015-02-18 | 清华大学深圳研究生院 | Silicon-carbon composite microsphere anode material and preparation method thereof |
| CN108511734A (en) * | 2018-05-18 | 2018-09-07 | 深圳市优特利电源有限公司 | The preparation method of Si-C composite material |
| CN109346681A (en) * | 2018-08-17 | 2019-02-15 | 福建翔丰华新能源材料有限公司 | A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof |
-
2019
- 2019-06-18 CN CN201910528246.9A patent/CN110289406B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362311A (en) * | 2014-09-23 | 2015-02-18 | 清华大学深圳研究生院 | Silicon-carbon composite microsphere anode material and preparation method thereof |
| CN108511734A (en) * | 2018-05-18 | 2018-09-07 | 深圳市优特利电源有限公司 | The preparation method of Si-C composite material |
| CN109346681A (en) * | 2018-08-17 | 2019-02-15 | 福建翔丰华新能源材料有限公司 | A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FANYU KON等: "Enhanced reversible Li-ion storage in Si@Ti3C2 MXene nanocomposite", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384381A (en) * | 2020-03-23 | 2020-07-07 | 北京化工大学 | Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof |
| CN111384381B (en) * | 2020-03-23 | 2021-06-15 | 北京化工大学 | Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof |
| CN112886019A (en) * | 2021-02-03 | 2021-06-01 | 山东大学 | High-stability three-dimensional MXene-COF-Li composite metal lithium negative electrode material and preparation method and application thereof |
| CN114242463A (en) * | 2021-11-19 | 2022-03-25 | 清华大学 | Anode active material, on-chip micro lithium ion capacitor comprising same and manufacturing method thereof |
| CN114242463B (en) * | 2021-11-19 | 2023-01-31 | 清华大学 | Anode active material, on-chip micro lithium ion capacitor comprising same and manufacturing method thereof |
| CN117362037A (en) * | 2023-10-16 | 2024-01-09 | 潍坊卓宇新材料科技有限公司 | Cadmium sulfide target piece processing technology and split processing die |
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