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1. 发明授权

US09660268B2 Alkali-ion battery with enhanced transition metal cyanometallate electrode structure 有权
公开(公告)号：US09660268B2
公开(公告)日：2017-05-23
申请号：US14928559
申请日：2015-10-30
申请人： Sharp Laboratories of America, Inc.
发明人： Jie Song , Yuhao Lu , Xin Zhao
IPC分类号： H01M4/00 , H01M4/58 , H01M4/62 , H01M2/16 , H01M10/054 , H01M4/38 , H01M4/56 , H01M4/136 , H01M4/1397 , H01M10/0585 , C01C3/11
CPC分类号： H01M4/5825 , C01C3/11 , H01M2/162 , H01M2/1626 , H01M2/1646 , H01M4/136 , H01M4/1397 , H01M4/381 , H01M4/387 , H01M4/56 , H01M4/622 , H01M4/623 , H01M10/054 , H01M10/0585
摘要： An alkali-ion battery is provided with a transition metal cyanometallate (TMCM) sheet cathode and a non-alkaline metal anode. The fabrication method mixes TMCM powders, conductive additives, and a polytetrafluoroethylene binder with a solution containing water, forming a wet paste. The wet paste is formed into a free-standing sheet of cathode active material, which is laminated to a cathode current collector, forming a cathode electrode. The free-standing sheet of cathode active material has a thickness typically in the range of 100 microns to 2 millimeters. The cathode electrode is assembled with a non-alkaline metal anode electrode and an ion-permeable membrane interposed between the cathode electrode and anode electrode, forming an assembly. The assembly is dried at a temperature of greater than 100 degrees C. The dried assembly is then inserted into a container (case) and electrolyte is added. Thick anodes made from free-standing sheets of active material can be similarly formed.

2. 发明授权

US09634317B2 Reactive separator for a metal-ion battery 有权
公开(公告)号：US09634317B2
公开(公告)日：2017-04-25
申请号：US14230882
申请日：2014-03-31
申请人： Sharp Laboratories of America, Inc.
发明人： Long Wang , Yuhao Lu
IPC分类号： H01M4/50 , H01M4/136 , H01M4/58 , C01C3/12 , H01M4/04 , H01M4/62 , H02J7/00 , H01M4/134 , H01M4/1395 , C01B17/02 , C01B19/02 , C01B25/00 , C01B31/00 , C01B33/021 , C01D1/02 , C01D15/02 , H01M4/131 , H01M4/133 , H01M4/1391 , H01M4/38 , H01M4/485 , H01M4/505 , H01M4/56 , H01M4/587 , H01M10/054 , H01M10/0525 , H01M10/0565 , H01M2/16 , H01M4/1397 , H01M2/14 , H01M10/056 , H01M10/052
CPC分类号： H01M4/134 , B01J6/008 , C01B17/02 , C01B19/02 , C01B25/003 , C01B32/00 , C01B33/021 , C01C3/12 , C01D1/02 , C01D15/02 , C01P2002/72 , C01P2002/77 , C01P2002/88 , H01M2/14 , H01M2/1653 , H01M2/1686 , H01M4/04 , H01M4/0404 , H01M4/0416 , H01M4/0452 , H01M4/0471 , H01M4/049 , H01M4/0495 , H01M4/0497 , H01M4/131 , H01M4/133 , H01M4/136 , H01M4/1391 , H01M4/1395 , H01M4/1397 , H01M4/366 , H01M4/38 , H01M4/381 , H01M4/382 , H01M4/387 , H01M4/485 , H01M4/505 , H01M4/56 , H01M4/58 , H01M4/5815 , H01M4/5825 , H01M4/587 , H01M4/60 , H01M4/623 , H01M4/628 , H01M10/052 , H01M10/0525 , H01M10/054 , H01M10/056 , H01M10/0565 , H01M2004/027 , H02J7/0042 , Y02E60/122 , Y10T29/49108
摘要： A reactive separator is provided for a metal-ion battery. The reactive separator is made up of a reactive layer that is chemically reactive to alkali or alkaline earth metals, and has a first side and a second side. A first non-reactive layer, chemically non-reactive with alkali or alkaline earth metals, is adjacent to the reactive layer first side. A second non-reactive layer, also chemically non-reactive with alkali or alkaline earth metals, is adjacent to the reactive layer second side. More explicitly, the first and second non-reactive layers are defined as having less than 5 percent by weight (wt %) of materials able to participate in electrochemical reactions with alkali or alkaline earth metals. The reactive layer may be formed as a porous membrane embedded with reactive components, where the porous membrane is carbon or a porous polymer. Alternatively, the reactive layer is formed as a polymer gel embedded with reactive components.

3. 发明授权

US09608268B2 Alkali and alkaline-earth ion batteries with non-metal anode and hexacyanometallate cathode 有权
公开(公告)号：US09608268B2
公开(公告)日：2017-03-28
申请号：US14699962
申请日：2015-04-29
申请人： Sharp Laboratories of America, Inc.
发明人： Yuhao Lu , Jong-Jan Lee , Motoaki Nishijima , Seizoh Kakimoto
IPC分类号： H01M4/58 , H01M4/04 , H01M4/139 , H01M10/054 , H01M10/36 , H01M4/136 , H01M4/587 , H01M4/02
CPC分类号： H01M4/58 , H01M4/0404 , H01M4/0438 , H01M4/0445 , H01M4/0459 , H01M4/136 , H01M4/139 , H01M4/587 , H01M10/054 , H01M10/36 , H01M2004/028 , Y02E60/122
摘要： A battery structure is provided for making alkali ion and alkaline-earth ion batteries. The battery has a hexacyanometallate cathode, a non-metal anode, and non-aqueous electrolyte. A method is provided for forming the hexacyanometallate battery cathode and non-metal battery anode prior to the battery assembly. The cathode includes hexacyanometallate particles overlying a current collector. The hexacyanometallate particles have the chemical formula A′n′AmM1xM2y(CN)6, and have a Prussian Blue hexacyanometallate crystal structure.

4. 发明授权

US09385370B2 Transition metal hexacyanoferrate battery with single plateau charge/discharge curve 有权
标题翻译：过渡金属六氰基铁铵电池具有单一平台充放电曲线
公开(公告)号：US09385370B2
公开(公告)日：2016-07-05
申请号：US14744476
申请日：2015-06-19
申请人： Sharp Laboratories of America, Inc.
发明人： Yuhao Lu , Hidayat Kisdarjono , Jong-Jan Lee , David Evans
IPC分类号： H01M4/58 , H01M4/136 , H02J7/00 , H01M10/054 , H01M10/0568 , H01M10/44 , H01M4/02
CPC分类号： H01M4/5825 , H01M4/136 , H01M4/58 , H01M4/625 , H01M10/054 , H01M10/0568 , H01M10/446 , H01M2004/028 , H02J7/0063 , H02J7/0068 , Y02E60/122
摘要： A transition metal hexacyanoferrate (TMH) cathode battery is provided. The battery has a AxMn[Fe(CN)6]y.zH2O cathode, where the A cations are either alkali or alkaline-earth cations, such as sodium or potassium, where x is in the range of 1 to 2, where y is in the range of 0.5 to 1, and where z is in the range of 0 to 3.5. The AxMn[Fe(CN)6]y.zH2O has a rhombohedral crystal structure with Mn2+/3+ and Fe2+/3+ having the same reduction/oxidation potential. The battery also has an electrolyte, and anode made of an A metal, an A composite, or a material that can host A atoms. The battery has a single plateau charging curve, where a single plateau charging curve is defined as a constant charging voltage slope between 15% and 85% battery charge capacity. Fabrication methods are also provided.
摘要翻译：提供了一种过渡金属六氰基铁酸盐（TMH）阴极电池。电池具有AxMn [Fe（CN）6] y.zH 2 O阴极，其中A阳离子是碱金属或碱土金属阳离子，如钠或钾，其中x在1至2的范围内，其中y为在0.5至1的范围内，其中z在0至3.5的范围内。 AxMn [Fe（CN）6] y.zH2O具有具有相同还原/氧化电位的Mn2 + / 3 +和Fe2 + / 3 +的菱方晶体结构。电池还具有电解质和由A金属，A复合材料或能够承载A原子的材料制成的阳极。电池具有单个平台充电曲线，其中单个平台充电曲线被定义为电池充电容量的15％至85％之间的恒定充电电压斜率。还提供制造方法。

5. 发明授权

US09246164B2 Protected transition metal hexacyanoferrate battery electrode 有权
标题翻译：保护过渡金属六氰基铁酸盐电池电极
公开(公告)号：US09246164B2
公开(公告)日：2016-01-26
申请号：US13872673
申请日：2013-04-29
申请人： Sharp Laboratories of America, Inc.
发明人： Yuhao Lu , Jong-Jan Lee , David Evans
IPC分类号： H01M4/136 , H01M4/36 , H01M4/58 , H01M4/1397 , H01M10/052 , H01M10/054 , H01M4/02
CPC分类号： H01M4/0404 , H01M4/0423 , H01M4/0428 , H01M4/136 , H01M4/1397 , H01M4/366 , H01M4/58 , H01M4/582 , H01M4/622 , H01M4/625 , H01M4/661 , H01M10/052 , H01M10/054 , H01M2004/028 , Y02E60/122
摘要： A protected transition metal hexacyanoferrate (TMHCF) battery cathode is presented, made from AxMyFez(CN)n.mH2O particles, where the A cations are either alkali or alkaline-earth cations, and M is a transition metal. In one aspect the cathode passivation layer may be materials such as oxides, simple salts, carbonaceous materials, or polymers that form a film overlying the AxMyFez(CN)n.mH2O particles. In another aspect, the cathode passivation layer is a material such as oxygen, nitrogen, sulfur, fluorine, chlorine, or iodine that interacts with the AxMyFez(CN)n.mH2O particles, to cure defects in the AxMyFez(CN)n.mH2O crystal lattice structure. Also presented are TMHCF battery synthesis methods.
摘要翻译：呈现由AxMyFez（CN）n.mH2O颗粒制成的受保护的过渡金属六氰基铁酸盐（TMHCF）电池阴极，其中A阳离子为碱金属或碱土金属阳离子，M为过渡金属。在一个方面，阴极钝化层可以是形成覆盖在AxMyFez（CN）n.mH2O颗粒上的膜的材料，例如氧化物，简单盐，碳质材料或聚合物。在另一方面，阴极钝化层是与AxMyFez（CN）n.mH2O颗粒相互作用的诸如氧，氮，硫，氟，氯或碘的材料，以固化AxMyFez（CN）n.mH2O中的缺陷晶格结构。还提出了TMHCF电池的合成方法。

6. 发明申请

US20150266745A1 Metal Cyanometallate Synthesis Method 审中-公开
标题翻译：金属氰酸金属盐合成方法
公开(公告)号：US20150266745A1
公开(公告)日：2015-09-24
申请号：US14731165
申请日：2015-06-04
申请人： Sharp Laboratories of America, Inc. , Board of Regents, The University of Texas System
发明人： Jie Song , Yuhao Lu , Long Wang
IPC分类号： C01C3/12
CPC分类号： C01C3/12 , H01M4/5825 , H01M10/054
摘要： A method is provided for synthesizing metal cyanometallate (MCM). The method provides a solution of AXM1Y(CN)Z; where “A” is selected from a first group of metals and M1 is selected from a second group of metals. The method adds a material including M2 to the solution to form a liquid phase material that may be either a suspension or a solution. M2 is selected from the second group of metals. The method adds acid to the liquid phase material. The addition of acid to the liquid phase material decomposes the M2 material into M2-ions. Simultaneous with the addition of the acid, a precipitate of ANM1PM2Q(CN)R.FH2O is formed, where N is in a range of 1 to 2. A variation of the above-described synthesis method is also provided.
摘要翻译：提供了合成氰基金属金属（MCM）的方法。该方法提供AXM1Y（CN）Z的溶液; 其中“A”选自第一组金属，M1选自第二组金属。该方法将包括M2的材料添加到溶液中以形成可以是悬浮液或溶液的液相材料。 M2选自第二组金属。该方法向液相材料中加入酸。将酸添加到液相材料中将M2材料分解成M2-离子。加入酸同时形成ANM1PM2Q（CN）R.FH2O的沉淀物，其中N在1〜2的范围内。还提供了上述合成方法的变化。

7. 发明申请

US20150263383A1 Electrolyte Additives for Transition Metal Cyanometallate Electrode Stabilization 有权
标题翻译：用于过渡金属氰酸金属电极稳定化的电解质添加剂
公开(公告)号：US20150263383A1
公开(公告)日：2015-09-17
申请号：US14320352
申请日：2014-06-30
申请人： Sharp Laboratories of America, Inc.
发明人： Yuhao Lu , Long Wang , Sean Vail
IPC分类号： H01M10/0567 , H02J7/00 , H01M4/38 , H01M10/44 , H01M10/054 , H01M4/58
CPC分类号： H01M10/0567 , H01M4/136 , H01M4/381 , H01M4/58 , H01M10/0525 , H01M10/054 , H01M10/0569 , H01M10/44 , H01M2300/0037 , Y10T29/49108
摘要： A method is provided for the self-repair of a transition metal cyanometallate (TMCM) battery electrode. The battery is made from a TMCM cathode, an anode, and an electrolyte including solution formed from a solvent and an alkali or alkaline earth salt. The electrolyte includes an additive represented as G-R-g: where G and g are independently include materials with nitrogen (N) sulfur (S), oxygen (O), or combinations of the above-recited elements; and where R is an alkene or alkane group. In response to charging and discharging the battery in a plurality of cycles, the method creates vacancies in a surface of the TMCM cathode. Then, the method fills the vacancies in the surface of the TMCM cathode with the electrolyte additive. An electrolyte and TMCM battery using the above-mentioned additives are also provided.
摘要翻译：提供了一种过渡金属氰金属（TMCM）电池电极的自修复方法。电池由TMCM阴极，阳极和包含由溶剂和碱金属或碱土金属盐形成的溶液的电解质制成。电解质包括以G-R-g表示的添加剂：其中G和g独立地包括具有氮（N）硫（S），氧（O）或上述元素的组合的材料; 并且其中R是烯烃或烷烃基团。响应于以多个周期对电池进行充电和放电，该方法在TMCM阴极的表面中产生空位。然后，该方法用电解质添加剂填充TMCM阴极表面的空位。还提供了使用上述添加剂的电解质和TMCM电池。

8. 发明申请

US20150200390A1 Transition Metal Cyanometallate Cathode Battery with Metal Plating Anode 有权
标题翻译：过渡金属金属阴极电池与金属电镀阳极
公开(公告)号：US20150200390A1
公开(公告)日：2015-07-16
申请号：US14668788
申请日：2015-03-25
申请人： Sharp Laboratories of America, Inc.
发明人： Yuhao Lu , Long Wang , Jong-Jan Lee
IPC分类号： H01M4/136 , H01M4/133 , H01M4/587 , H01M4/137
CPC分类号： H01M4/136 , C01C3/12 , H01M4/0404 , H01M4/0452 , H01M4/1397 , H01M4/58 , H01M4/661 , H01M4/663 , H01M4/667 , H01M4/668 , H01M10/054 , Y02E60/122
摘要： A method is provided for cycling power in a transition metal cyanometallate (TMCM) cathode battery. The method provides a battery with a TMCM cathode, an anode, and an electrolyte, where TMCM corresponds to the chemical formula of AXM1NM2M(CN)Y-d(H2O), where “A” is an alkali or alkaline earth metal, and where M1 and M2 are transition metals. The method charges the battery using a first charging current, or greater. In response to the charging current, a plating of “A” metal is formed overlying a plating surface of the anode. In response to discharging the battery, the “A” metal plating is removed from the anode plating surface. In one aspect, in an initial charging of the battery, a permanent solid electrolyte interphase (SEI) layer is formed overlying the anode plating surface. In subsequent charging and discharging cycles, the permanent SEI layer is maintained overlying the anode plating surface.
摘要翻译：提供了一种在过渡金属氰金属（TMCM）阴极电池中循环功率的方法。该方法提供具有TMCM阴极，阳极和电解质的电池，其中TMCM对应于AXM1NM2M（CN）Yd（H2O）的化学式，其中“A”是碱金属或碱土金属，并且其中M1和 M2是过渡金属。该方法使用第一充电电流或更高的电池充电。响应于充电电流，在阳极的电镀表面上形成覆盖“A”金属的电镀。响应于电池的放电，从阳极电镀表面去除“A”金属电镀。一方面，在电池的初始充电中，在阳极电镀表面上形成永久的固体电解质相（SEI）层。在随后的充放电循环中，永久性SEI层保持覆盖阳极电镀表面。

9. 发明申请

US20140186707A1 Battery with an Anode Preloaded with Consumable Metals 有权
标题翻译：带有负载有消耗性金属的阳极的电池
公开(公告)号：US20140186707A1
公开(公告)日：2014-07-03
申请号：US14198702
申请日：2014-03-06
申请人： Sharp Laboratories of America, Inc.
发明人： Yuhao Lu , Long Wang , Jong-Jan Lee
IPC分类号： H01M4/136 , H01M10/054 , H01M4/134 , H01M4/131 , H01M4/133
CPC分类号： H01M4/134 , B01J6/008 , C01B17/02 , C01B19/02 , C01B25/003 , C01B32/00 , C01B33/021 , C01C3/12 , C01D1/02 , C01D15/02 , C01P2002/72 , C01P2002/77 , C01P2002/88 , H01M2/14 , H01M2/1653 , H01M2/1686 , H01M4/04 , H01M4/0404 , H01M4/0416 , H01M4/0452 , H01M4/0471 , H01M4/049 , H01M4/0495 , H01M4/0497 , H01M4/131 , H01M4/133 , H01M4/136 , H01M4/1391 , H01M4/1395 , H01M4/1397 , H01M4/366 , H01M4/38 , H01M4/381 , H01M4/382 , H01M4/387 , H01M4/485 , H01M4/505 , H01M4/56 , H01M4/58 , H01M4/5815 , H01M4/5825 , H01M4/587 , H01M4/60 , H01M4/623 , H01M4/628 , H01M10/052 , H01M10/0525 , H01M10/054 , H01M10/056 , H01M10/0565 , H01M2004/027 , H02J7/0042 , Y02E60/122 , Y10T29/49108
摘要： A method is provided for fabricating a battery using an anode preloaded with consumable metals. The method forms an ion-permeable membrane immersed in an electrolyte. A preloaded anode is immersed in the electrolyte, comprising MeaX, where X is a material such as carbon, metal capable of being alloyed with Me, intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials. Me is a metal such as alkali metals, alkaline earth metals, and combinations of the above-listed metals. A cathode is also immersed in the electrolyte and separated from the preloaded anode by the ion-permeable membrane. The cathode comprises M1YM2Z(CN)N.MH2O. After a plurality of initial charge and discharge operations are preformed, an anode is formed comprising MebX overlying the current collector in a battery discharge state, where 0≦b
摘要翻译：提供了一种使用预负载有可消耗金属的阳极来制造电池的方法。该方法形成浸入电解质中的离子渗透膜。将预加载的阳极浸入包含MeaX的电解质中，其中X是诸如碳的材料，能够与Me合金化的金属，插层氧化物，电化学活性的有机化合物以及上述材料的组合。 Me是金属，例如碱金属，碱土金属和上述金属的组合。阴极也浸入电解质中，并通过离子透过膜与预载阳极分离。阴极包括M1YM2Z（CN）N.MH2O。在进行多次初始充电和放电操作之后，在电池放电状态下形成包含覆盖在集电体上的MebX的阳极，其中0＆lt; nlE; b

10. 发明申请

US20140186706A1 Battery Anode with Preloaded Metals 有权
标题翻译：带负载金属的电池阳极
公开(公告)号：US20140186706A1
公开(公告)日：2014-07-03
申请号：US14198663
申请日：2014-03-06
申请人： Sharp Laboratories of America, Inc.
发明人： Long Wang , Yuhao Lu , Jong-Jan Lee
IPC分类号： H01M4/136 , H01M4/04 , C01B31/00 , C01B25/00 , C01B17/02 , C01B33/021 , C01B19/02 , C01D15/02 , C01D1/02 , H01M4/1395 , H01M4/1391 , H01M4/133 , H01M4/485 , H01M4/505 , H01M4/131 , H01M4/134 , H01M4/56 , H01M4/58 , H01M4/587 , H01M4/38
CPC分类号： H01M4/134 , B01J6/008 , C01B17/02 , C01B19/02 , C01B25/003 , C01B32/00 , C01B33/021 , C01C3/12 , C01D1/02 , C01D15/02 , C01P2002/72 , C01P2002/77 , C01P2002/88 , H01M2/14 , H01M2/1653 , H01M2/1686 , H01M4/04 , H01M4/0404 , H01M4/0416 , H01M4/0452 , H01M4/0471 , H01M4/049 , H01M4/0495 , H01M4/0497 , H01M4/131 , H01M4/133 , H01M4/136 , H01M4/1391 , H01M4/1395 , H01M4/1397 , H01M4/366 , H01M4/38 , H01M4/381 , H01M4/382 , H01M4/387 , H01M4/485 , H01M4/505 , H01M4/56 , H01M4/58 , H01M4/5815 , H01M4/5825 , H01M4/587 , H01M4/60 , H01M4/623 , H01M4/628 , H01M10/052 , H01M10/0525 , H01M10/054 , H01M10/056 , H01M10/0565 , H01M2004/027 , H02J7/0042 , Y02E60/122 , Y10T29/49108
摘要： A method is presented for fabricating an anode preloaded with consumable metals. The method provides a material (X), which may be one of the following materials: carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials. The method loads the metal (Me) into the material (X). Typically, Me is an alkali metal, alkaline earth metal, or a combination of the two. As a result, the method forms a preloaded anode comprising Me/X for use in a battery comprising a M1YM2Z(CN)N·MH2O cathode, where M1 and M2 are transition metals. The method loads the metal (Me) into the material (X) using physical (mechanical) mixing, a chemical reaction, or an electrochemical reaction. Also provided is preloaded anode, preloaded with consumable metals.
摘要翻译：提出了一种用于制造预先装有消耗性金属的阳极的方法。该方法提供材料（X），其可以是以下材料之一：碳，能够与金属（Me），嵌入氧化物，电化学活性有机化合物和上述材料的组合进行电化学合金化的金属。该方法将金属（Me）加载到材料（X）中。通常，Me是碱金属，碱土金属或两者的组合。结果，该方法形成包含Me / X的预负载阳极，用于包含M1YM2Z（CN）N·MH2O阴极的电池，其中M1和M2是过渡金属。该方法使用物理（机械）混合，化学反应或电化学反应将金属（Me）加载到材料（X）中。还提供预负载阳极，预装有消耗性金属。

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