CN104150543A - Cu<2+>, Ce<4+>, Ag<+> doped iron fluoride composite positive pole material and preparation method thereof - Google Patents
Cu<2+>, Ce<4+>, Ag<+> doped iron fluoride composite positive pole material and preparation method thereof Download PDFInfo
- Publication number
- CN104150543A CN104150543A CN201410348459.0A CN201410348459A CN104150543A CN 104150543 A CN104150543 A CN 104150543A CN 201410348459 A CN201410348459 A CN 201410348459A CN 104150543 A CN104150543 A CN 104150543A
- Authority
- CN
- China
- Prior art keywords
- weight percent
- mentioned
- positive pole
- salt
- preparation
- 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
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a Cu<2+>, Ce<4+>, Ag<+> doping modified iron fluoride positive pole material and a preparation method thereof. The method comprises the following step: performing ball milling on copper salt, cerium salt, silver salt and synthesis raw materials in a high-energy ball mill for a certain time, and performing heat treatment to obtain the FeF3 positive pole material. The Cu<2+> partially occupies iron ions of FeF3 for coordination, thereby being beneficial to increase the discharge potential and improve the energy density; the high-valence Ce<4+> is doped, thereby being beneficial to increase the specific capacity of the material; and the Ag<2+> is doped, thereby reducing the conversion reaction activation energy during charge. Thus, the invention is beneficial to improve the rate characteristic and energy density, thereby improving the comprehensive electrochemical property of the material.
Description
Technical field
The present invention relates to a kind of heavy body ferric fluoride complex lithium electricity positive electrode material manufacture method technical field.
Background technology
Lithium-ion secondary cell have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density, in global portable power source market, have at present and surpass 30,000,000,000 dollars of/year shares and increase gradually to surpass 10% speed.Particularly in recent years, along with petering out of fossil energy, the new forms of energy such as sun power, wind energy, biomass energy become the alternative of traditional energy gradually, and wherein wind energy, sun power have intermittence, for meeting lasting supply of electric power needs, use a large amount of energy-storage batteries simultaneously; The urban air-quality problem that vehicle exhaust brings is day by day serious, and instant stage has been arrived in vigorously advocating and developing of power truck (EV) or hybrid electric vehicle (HEV); These demands provide lithium ion battery explosive growth point, also the performance of lithium ion battery are had higher requirement simultaneously.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal that scientific and technical personnel study, and the research and development of heavy body positive electrode material can alleviate that current lithium ion battery group volume is large, heavy weight, price are high-leveled and difficult to meet the situation of high power consumption and high-power equipment needs.Yet since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode material is hovered all the time between 100-180mAh/g, the low bottleneck that promotes lithium ion battery specific energy that become of positive electrode material specific storage.The current commercial lithium ion battery the most widely positive electrode material of practicality is LiCoO
2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore in recent years, the researchist of countries in the world is devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, up till now, the lithium ion cell positive filtering out reaches tens of kinds, but really have potential commercial applications prospect or the positive electrode material that appeared on market very few really.As lithium manganate having spinel structure LiMn
2o
4, its cost is lower, and than being easier to preparation, safety performance is also relatively good, however capacity is lower, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation hold facility is not good, and under high temperature, capacity attenuation is very fast, Mn
3+john-Teller effect and the dissolving in ionogen perplexing for a long time researchist.The LiNiO of laminate structure
2and LiMnO
2although there is larger theoretical specific capacity, be respectively 275mAh/g and 285mAh/g, their preparations are very difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is very fast.And business-like iron lithium phosphate LiFePO progressively at present
4cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity approximately only has 170mAh/g, and actual capacity is in 140mAh/g left and right [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1:123-128.].There is at present the positive electrode material that surpasses 200mAh/g specific storage of market outlook to only have lithium vanadate Li
1+xv
3o
8, Li
1+xv
3o
8material can have and has the capacity that even approaches 300mAh/g, but its electric discharge average voltage is lower and also production process in barium oxide often toxicity is larger.High lithium is than on positive electrode material in recent years, particularly the high lithium of manganese base manganese-nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system compares positive electrode material, have surpass 200mAh/g volume ratio, compared with high thermostability, receive people's concern with relative cheap cost, yet the performance under this material high magnification is very undesirable, limited its application [Young-Sik Hong, Yong Joon Park in power cell, et al., Solid State Ionics, 2005,176:1035-1042].
In recent years, FeF
3material is because its capacity is high, the low visual field that enters investigator of the prices of raw and semifnished materials.FeF
3the principle of work of material and traditional anode material for lithium-ion batteries is different, traditional lithium ion cell positive and negative pole all exist lithium ion to embed or the space of de-embedding, and lithium ion in ionogen embeds back and forth between positive pole and negative pole and de-embedding and " rocking chair " battery of discharging and proposing as Armand etc.And FeF
3a kind of transition material, namely in whole discharge process, FeF
3there is following variation [Badway F, Cosandey F, Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10): A1318-A1327.]:
Li
++FeF
3+e→LiFeF
3----(1)
LiFeF
3+2Li
++2e→3LiF+Fe-(2)
The first step and the namely lithium ion embedding of traditional lithium ion, in whole reaction process, lattice does not have large variation; And second replacement(metathesis)reaction that is metal, there is conversion completely in parent lattice.The theoretical capacity of the first step is 237mAh.g
-1; Complete reaction can realize the conversion of 3 electronics, and the theoretical capacity of subordinate phase is 474mAh.g
-1; Total volume is 711mAh.g
-1; Although this material does not have clear and definite discharge platform, average discharge voltage is also lower, and it approaches 800mAh.g
-1theoretical specific capacity still obtained the attention of investigation of materials personnel height.Yet, pass through as Arai Amatucci[Badway F, Pereira N, Cosandey F, et al., J.Electrochem.Soc., 2003,150 (9): A1209-A1218.] etc. scholar's research is found, its theoretical capacity major part be discharged not is an easy thing.First FeF
3the non-constant of electronic conduction ability, simultaneously its lithium ion conductivity is also very low, and the product LiF after conversion is electronic body, the ability of conductive lithium ion is also very poor simultaneously, thereby has caused FeF
3the useful capacity that material can utilize is lower, and charging and discharging currents is little, and multiplying power property is poor; Polarization in charge and discharge process is comparatively serious, and charging/discharging voltage platform has a long way to go; Capacitance reserve ability is not good, and along with discharging and recharging the increase of number of times, capacity attenuation is serious.In research, can only discharge in early days about 50-100 mAh.g
-1reversible capacity; Amatucci etc. had improved its conductive capability by forming carbon/ferric fluoride nano-complex (CMFNCs) with carbon material through long-time high-energy ball milling afterwards, had greatly improved its chemical property, and its loading capacity can reach 200 mAh.g
-1left and right [Badway F, Mansour A.N, Pereira N, et al., Chem.Mater., 2007,19 (17): 4129-4141.].But carbon material adhering on positive electrode material particle surface mainly leaned on physical adsorption, complete carbonaceous conductive link is more difficult.At this, as previously mentioned, the sparking voltage of this material is lower, and effectively energy density is not too outstanding; Finally, because FeF
3material is slightly soluble in cold water, so conventionally adopt the method preparation of ethanol liquid phase, needs to use a large amount of ethanol in building-up process, and economy is not good.Be unsuitable in industrial applications.
Therefore, improve FeF
3the chemical property of positive electrode material need to be sought a kind of method that can improve lithium ion conductivity and energy density, makes that preparation flow is simple as far as possible, cost is low, convenient and swift simultaneously, and this is to FeF
3the development and application of positive electrode material is particularly important.
Summary of the invention
The present invention is directed to existing background technology and proposed a kind of Cu2
+, Ce
4+, Ag
+doping vario-property ferric fluoride anode material and preparation method.The method obtains FeF by mantoquita, cerium salt, silver salt and synthesis material in high energy ball mill after ball milling thermal treatment after a while
3positive electrode material.Cu2
+by part, occupy FeF
3iron ion coordination, contributes to improve its discharge potential, improves energy density; And by high price Ce
4+adulterate, contribute to improve the specific storage of material; Pass through Ag
+doping, while reducing charging, conversion reaction activation energy, contributes to like this to improve its multiplying power property, energy density and cycle performance, thereby improves the comprehensive electrochemical of this material.
Cu
2+, Ce
4+, Ag
+doping vario-property ferric fluoride anode material and preparation method; it is characterized in that containing crystal water molysite and Neutral ammonium fluoride, (mol ratio is 1.0: 3.0-3.6) with weight percent be 3-15% mantoquita, cerium salt, silver salt, the weight percent ethanol that is 0.1-3.0%, the auxiliary agent that weight percent is 0.5-3.0%; normal temperature ball milling after 5-20 hour under atmosphere protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300-450 degree constant temperature cooling after 2-10 hour, prepare Cu2
+, Ce
4+, Ag
+the FeF of doping vario-property
3composite positive pole.
Above-mentioned is Fe (NO containing crystal water molysite
3)
39H
2o, FeCl
36H
2o and Fe
2(SO
4)
39H
2a kind of in O;
Above-mentioned mantoquita is Cu (C
2o
4) 0.5H
2o, Cu (NO
3)
23H
2o and CuSO
45H
2a kind of in O;
Above-mentioned cerium salt is Ce (NH
4)
2(NO
3)
6;
Above-mentioned silver salt is AgNO
3;
Above-mentioned auxiliary agent is tween-80, a kind of in span-60 and tx-10;
Above-mentioned atmosphere is high pure nitrogen or high-purity argon gas;
Fig. 1 is charging capacity, loading capacity and the efficiency for charge-discharge figure of front 10 circulations of this material, voltage range 2.0V-4.0V, charging and discharging currents 0.1C.
Compared with prior art, the invention has the advantages that: Cu
2+by part, occupy FeF
3iron ion coordination, contributes to improve its discharge potential, improves energy density; And by high price Ce
4+adulterate, contribute to improve the specific storage of material; Pass through Ag
+doping, conversion reaction activation energy while reducing charging; Pass through Cu
2+, Ce
4+, Ag
+thereby codoped improves the comprehensive electrochemical of this material.
Accompanying drawing explanation
Charging capacity, loading capacity and the efficiency for charge-discharge figure of front 10 circulations of this material of Fig. 1, voltage range 2.0V-4.0V, charging and discharging currents 0.1C.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by Fe (NO
3)
39H
2cu (the C that O and Neutral ammonium fluoride (mol ratio is 1.0: 3.2) and weight percent are 3.2%
2o
4) 0.5H
2ce (the NH that O, weight percent are 3%
4)
2(NO
3)
6, the weight percent AgNO that is 4%
3, the weight percent tween-80 that is 0.6% and the weight percent ethanol that is 0.5% normal temperature ball milling after 5 hours under high pure nitrogen protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 450 degree constant temperature cooling after 3 hours, prepare Cu
2+, Ce
4+, Ag
+the FeF of doping vario-property
3positive electrode material.
Embodiment 2: by FeCl
36H
2cu (the C that O and Neutral ammonium fluoride (mol ratio is 1.0: 3.6) and weight percent are 6.5%
2o
4) 0.5H
2ce (the NH that O, weight percent are 13%
4)
2(NO
3)
6, the weight percent AgNO that is 8%
3, the weight percent span-60 that is 0.9% and the weight percent ethanol that is 1.0% normal temperature ball milling after 20 hours under high pure nitrogen protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 400 degree constant temperature cooling after 6.5 hours, prepare Cu
2+, Ce
4+, Ag
+the FeF of doping vario-property
3positive electrode material.
Embodiment 3: by Fe
2(SO
4)
39H
2cu (the NO that O and Neutral ammonium fluoride (mol ratio is 1.0: 3.5) and weight percent are 15%
3)
23H
2ce (the NH that O, weight percent are 7.5%
4)
2(NO
3)
6, the weight percent AgNO that is 13%
3, the weight percent tween-80 that is 1.5% and the weight percent ethanol that is 2.0% normal temperature ball milling after 10 hours under high-purity argon gas protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 350 degree constant temperature cooling after 8.5 hours, prepare Cu2
+, Ce
4+, Ag
+the FeF of doping vario-property
3positive electrode material.
Embodiment 4: by FeCl
36H
2the CuSO that O and Neutral ammonium fluoride (mol ratio is 1.0: 3.3) and weight percent are 8%
45H
2ce (the NH that O, weight percent are 5.5%
4)
2(NO
3)
6, the weight percent AgNO that is 6%
3, the weight percent tx-10 that is 3.0% and the weight percent ethanol that is 3.0% normal temperature ball milling after 15 hours under high-purity argon gas protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 450 degree constant temperature cooling after 10 hours, prepare Cu
2+, Ce
4+, Ag
+the FeF of doping vario-property
3positive electrode material.
Embodiment 5: by Fe (NO
3)
39H
2the CuSO that O and Neutral ammonium fluoride (mol ratio is 1.0: 3.5) and weight percent are 8%
45H
2ce (the NH that O, weight percent are 5.6%
4)
2(NO
3)
6, the weight percent AgNO that is 11%
3, the weight percent span-60 that is 2.0% and the weight percent ethanol that is 0.1% normal temperature ball milling after 12 hours under high pure nitrogen protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300 degree constant temperature cooling after 6 hours, prepare Cu
2+, Ce
4+, Ag
+the FeF of doping vario-property
3positive electrode material.
Claims (7)
1. a Cu2
+, Ce
4+, Ag
+doping ferric fluoride composite positive pole and preparation method; it is characterized in that containing crystal water molysite and Neutral ammonium fluoride, (mol ratio is 1.0: 3.0-3.6) with weight percent be 3-15% mantoquita, cerium salt, silver salt, the weight percent ethanol that is 0.1-3.0%, the auxiliary agent that weight percent is 0.5-3.0%; normal temperature ball milling after 5-20 hour under atmosphere protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300-450 degree constant temperature cooling after 2-10 hour, prepare Cu2
+, Ce
4+, Ag
+the FeF of doping vario-property
3composite positive pole.
2. method according to claim 1, is characterized in that above-mentioned is Fe (NO containing crystal water molysite
3)
39H
2o, FeCl
36H
2o and Fe
2(SO
4)
39H
2a kind of in O.
3. method according to claim 1, is characterized in that above-mentioned mantoquita is Cu (C
2o
4) 0.5H
2o, Cu (NO
3)
23H
2o and CuSO
45H
2a kind of in O.
4. above-mentioned cobalt salt is Ce (NH
4)
2(NO
3)
6.
5. above-mentioned silver salt is AgNO
3.
6. method according to claim 1, is characterized in that above-mentioned auxiliary agent is tween-80, a kind of in span-60 and tx-10.
7. method according to claim 1, is characterized in that above-mentioned atmosphere is high pure nitrogen or high-purity argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410348459.0A CN104150543B (en) | 2014-07-14 | 2014-07-14 | A kind of Cu 2+, Ce 4+, Ag +doping ferric fluoride composite positive pole and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410348459.0A CN104150543B (en) | 2014-07-14 | 2014-07-14 | A kind of Cu 2+, Ce 4+, Ag +doping ferric fluoride composite positive pole and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104150543A true CN104150543A (en) | 2014-11-19 |
| CN104150543B CN104150543B (en) | 2016-04-20 |
Family
ID=51876214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410348459.0A Active CN104150543B (en) | 2014-07-14 | 2014-07-14 | A kind of Cu 2+, Ce 4+, Ag +doping ferric fluoride composite positive pole and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104150543B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104795536A (en) * | 2015-04-19 | 2015-07-22 | 宁波大学 | Bismuth fluoride lithium ion cell anode material prepared through liquid phase synthesis and having B<3+> and La<3+> doped orthorhombic structure and preparation method of bismuth fluoride lithium ion cell anode material |
| CN104795539A (en) * | 2015-04-19 | 2015-07-22 | 宁波大学 | Cathode material for laminar bismuth fluoride lithium ion battery of liquid phase synthesis Cu2+, fe3+doped sheet and its prepn |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4938945A (en) * | 1988-10-18 | 1990-07-03 | Pennwalt Corporation | High purity anhydrous FeF3 and process for its manufacture |
| CN103165888A (en) * | 2013-03-02 | 2013-06-19 | 合肥国轩高科动力能源股份公司 | Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity |
| CN103199253A (en) * | 2013-03-31 | 2013-07-10 | 马军昌 | Preparation method of graphene-ferric fluoride composite cathode material |
| CN103515598A (en) * | 2013-09-18 | 2014-01-15 | 宁波大学 | Aluminum zirconium acid ester-doped titanium phosphate double-component surface-modified ferric fluoride anode material and preparation method |
-
2014
- 2014-07-14 CN CN201410348459.0A patent/CN104150543B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4938945A (en) * | 1988-10-18 | 1990-07-03 | Pennwalt Corporation | High purity anhydrous FeF3 and process for its manufacture |
| CN103165888A (en) * | 2013-03-02 | 2013-06-19 | 合肥国轩高科动力能源股份公司 | Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity |
| CN103199253A (en) * | 2013-03-31 | 2013-07-10 | 马军昌 | Preparation method of graphene-ferric fluoride composite cathode material |
| CN103515598A (en) * | 2013-09-18 | 2014-01-15 | 宁波大学 | Aluminum zirconium acid ester-doped titanium phosphate double-component surface-modified ferric fluoride anode material and preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104795536A (en) * | 2015-04-19 | 2015-07-22 | 宁波大学 | Bismuth fluoride lithium ion cell anode material prepared through liquid phase synthesis and having B<3+> and La<3+> doped orthorhombic structure and preparation method of bismuth fluoride lithium ion cell anode material |
| CN104795539A (en) * | 2015-04-19 | 2015-07-22 | 宁波大学 | Cathode material for laminar bismuth fluoride lithium ion battery of liquid phase synthesis Cu2+, fe3+doped sheet and its prepn |
| CN104795536B (en) * | 2015-04-19 | 2017-08-29 | 宁波大学 | A kind of liquid phase synthesis B3+, La3+Orthohormbic structure of adulterating fluorination bismuth anode material for lithium-ion batteries and preparation method thereof |
| CN104795539B (en) * | 2015-04-19 | 2017-08-29 | 宁波大学 | A kind of liquid phase synthesis Cu2+,Fe3+Sheet of adulterating fluorination bismuth anode material for lithium-ion batteries and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104150543B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20120264018A1 (en) | Composite positive electrode material with core-shell structure for lithium ion batteries and preparing method thereof | |
| CN104891570A (en) | Liquid phase synthetic Zr<4+> doped bismuth fluoride lithium-ion battery positive electrode material and preparation method thereof | |
| CN103700814B (en) | A kind of carbon solid acid aluminum zirconate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation method | |
| CN104150542B (en) | A Cu2+, co2+, ag+doped iron fluoride composite anode material and its preparation method | |
| CN104176785B (en) | A kind of Cu2+,Co2+,Ce4+,Ag+Doping ferric flouride composite positive pole and preparation method | |
| CN104795538B (en) | A kind of oxygen-containing fluorination bismuth anode material for lithium-ion batteries of synthesis in solid state and preparation method thereof | |
| CN104157836B (en) | A kind of Cu2+, Co2+, Zr4+, Ag+doping ferric flouride composite positive pole and preparation method | |
| CN104150543B (en) | A kind of Cu 2+, Ce 4+, Ag +doping ferric fluoride composite positive pole and preparation method | |
| CN103500830B (en) | A kind of nitrogen doped silicon carbide assisted Solid-state one-step method ferric flouride lithium electricity positive electrode and preparation method | |
| CN103682267B (en) | A kind of carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods | |
| CN103515598B (en) | The two component surface modification ferric fluoride anode materials of a kind of aluminium zirconate doping phosphoric acid titanium lithium and preparation method | |
| CN103500810B (en) | A kind of carbon solid acid borate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods | |
| CN105914347A (en) | Fe2O3/FeF3-2xOx/Fe<3+>,Co<2+> doped bismuth fluoride layer structure positive electrode material of lithium battery and preparation method thereof | |
| CN105914348A (en) | Bi<3+>,B<3+> doped copper fluoride positive electrode material coated by gradient structure and used for lithium battery and preparation method thereof | |
| CN102544497A (en) | Cathode material for lithium-ion secondary battery, preparation method for cathode material, lithium-ion secondary battery cathode and lithium-ion secondary battery | |
| CN103490048B (en) | The two component surface modification ferric fluoride anode materials of a kind of titanate esters doping phosphoric acid titanium lithium and preparation method | |
| CN103500818B (en) | The two component surface modification ferric fluoride anode materials of a kind of Aluminate doping phosphoric acid titanium lithium and preparation method | |
| CN104157837B (en) | A kind of Cu2+, Mn2+, Zr4+, Ag+ doping ferric flouride composite positive pole and preparation method | |
| CN103500817B (en) | A kind of silane doping phosphoric acid titanium lithium double-component surface-modified ferric fluoride anode and preparation method | |
| CN103500834B (en) | The two component surface modification ferric fluoride anode materials of a kind of borate doping phosphoric acid titanium lithium and preparation method | |
| CN103490068B (en) | A kind of carboxyl carbon titanate esters doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods | |
| CN105742632A (en) | Gradient structure coated Fe<3+> and B<3+> doping copper fluoride lithium battery positive electrode material and preparation method thereof | |
| CN105742604A (en) | Lithium battery cathode material with Bi2O3/BiF<3-2x>O<x>/Bi<3+> and Mg<2+> doping ferric fluoride layer structure and preparation method of lithium battery positive electrode material | |
| CN105914350A (en) | Fe2O3/FeF3-2xOx/Fe<3+>,Ce<4+> doped zirconium fluoride layer structure positive electrode material of lithium battery and preparation method thereof | |
| CN103500816B (en) | A kind of carbon solid acid silane doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200102 Address after: 313000 No.5-8, Changhe Road, Huaxi street, Changxing County, Huzhou City, Zhejiang Province Patentee after: Zhejiang Changxing green battery technology Co.,Ltd. Address before: Room 1,020, Nanxun Science and Technology Pioneering Park, No. 666 Chaoyang Road, Nanxun District, Huzhou City, Zhejiang Province, 313000 Patentee before: Huzhou You Yan Intellectual Property Service Co.,Ltd. Effective date of registration: 20200102 Address after: Room 1,020, Nanxun Science and Technology Pioneering Park, No. 666 Chaoyang Road, Nanxun District, Huzhou City, Zhejiang Province, 313000 Patentee after: Huzhou You Yan Intellectual Property Service Co.,Ltd. Address before: Box No. 29 No. 818 315211 Ningbo University Zhejiang province Ningbo City Fenghua Road, Jiangbei District Patentee before: Ningbo University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200917 Address after: Room 501, Office Building of Market Supervision Bureau of Langchuan Avenue, Jianping Town, Langxi County, Xuancheng City, Anhui Province Patentee after: Langxi pinxu Technology Development Co.,Ltd. Address before: 313000 No.5-8, Changhe Road, Huaxi street, Changxing County, Huzhou City, Zhejiang Province Patentee before: Zhejiang Changxing green battery technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221209 Address after: 276000 west of jiangouya village, Luoxi street, high tech Zone, Linyi City, Shandong Province Patentee after: SHANDONG GEXIN PRECISION CO.,LTD. Address before: Room 501, office building, Langchuan Avenue, Jianping Town, Langxi County, Xuancheng City, Anhui Province Patentee before: Langxi pinxu Technology Development Co.,Ltd. |
|
| TR01 | Transfer of patent right |